N2-phenylamidine derivatives

ABSTRACT

The invention provides fungicidal compounds of formula (I) and salts thereof wherein: R 1  is alkyl, alkenyl, alkynyl, carbocyclyl or heterocyclyl, each of which may be substituted, or hydrogen; R 2  and R 3 , which may be the same or different, are any group defined for R 1 ; cyano; acyl; —OR a  or —SR a , where R a  is alkyl, alkenyl, alkynyl, carbocyclyl or heterocyclyl, each of which may be substituted; or R 2  and R 3 , or R 2  and R 1 , together with their interconnecting atoms may form a ring, which may be substituted; R 4  is alkyl, alkenyl, alkynyl, carbocyclyl or heterocyclyl, each of which may be substituted; hydroxy; mercapto; azido; nitro; halogen; cyano; acyl; optionally substituted amino; cyanato; thiocyanato; —SF 5 ; —OR a ; —SR a  or —Si(R a ) 3 ; m is 0 to 3; when present R 5 , which may be the same or different to any other R 5 , is any group defined for R 4 ; R 6  is optionally substituted carbo- or heterocylclyl; and A is a defined linking group, or —A—R 6  and R 5  together with benzene ring M form an optionally substituted fused ring system.

This invention relates to the use of compounds as fungicides.

WO 95/22532 relates to substituted phenyltriazolinones claimed asherbicides and discloses inter alia a compound of formula A for whichthere is no characterising data therein.

The abstract, composition claim and use claim refer only to the use ofsuch compounds as herbicides and indeed the description supports theinvention only with herbicidal activity data. There is a sentence in thespecification that states that certain compounds show fungicidalactivity, although no fungicidal activity data are provided. Noindication is given as to which compounds are fungicidal and there is nosuggestion that compound A could be fungicidal.

We have now found that certain amidines have fungicidal activity.Therefore, the invention provides the use of a compound of generalformula I and salts thereof as fungicides

-   -   wherein    -   R¹ is alkyl, alkenyl, alkynyl, carbocyclyl or heterocyclyl, each        of which may be substituted, or hydrogen;    -   R² and R³, which may be the same or different, are any group        defined for R¹; cyano; acyl; —OR^(a) or —SR^(a), where R^(a) is        alkyl, alkenyl, alkynyl, carbocyclyl or heterocyclyl, each of        which may be substituted; or R² and R³, or R² and R¹, together        with their interconnecting atoms may form a ring, which may be        substituted;    -   R⁴ is alkyl, alkenyl, alkynyl, carbocyclyl or heterocyclyl, each        of which may be substituted; hydroxy; mercapto; azido; nitro;        halogen; cyano; acyl;    -   optionally substituted amino; cyanato; thiocyanato; —SF₅;        —OR^(a); —SR^(a) or —Si(R^(a))₃;    -   m is 0 to 3;    -   when present R⁵, which may be the same or different to any other        R⁵, is any group defined for R⁴;    -   R⁶ is optionally substituted carbo- or heterocyclyl; and    -   A is a direct bond, —O—, —S(O)_(n)—, —NR⁹—, —CR⁷═CR⁷—, —C≡C—,        —A¹—, —A¹—A¹—, —O—(A¹)_(k)—O—, —O—(A¹)_(k)—, —A³—, —A⁴—, —A¹O—,        —A¹S(O)_(n)—, —A²—, OA²—, —NR⁹A²—, —OA²—A¹—, —OA²—C(R⁷)═C(R⁸)—,        —S(O)_(n) A¹—, —A¹—A⁴—, —A¹—A⁴—C(R⁸)═N—N═CR⁸—,        —A¹—A⁴—C(R⁸)═N—X²—X³—, —A¹—A⁴—A³—, —A¹—A⁴—N(R⁹)—, —A¹—A⁴—X—CH₂—,        —A¹—A⁴—A¹—, —A¹—A⁴—CH₂X—, —A¹—A⁴—C(R⁸)═N—X²—X³—X¹—,        —A¹—X—C(R⁸)═N—, —A¹—X—C(R⁸)═N—N═CR⁸—, —A¹—X—C(R⁸)═N—N(R⁹)—,        —A¹—X—A²—X¹—, —A¹—O—A³, —A¹—O—C(R⁷)═C(R⁸)—,        —A¹—O—N(R⁹)—A²—N(R⁹)—, —A¹—O—N(R⁹)—A²—, —A¹—NR⁹)—A²—N(R⁹)—,        —A¹—N(R⁹)—A²—, —A¹—N(R⁹)—N═C(R⁸)—, —A³—A¹—, —A⁴—A³—, —A²—NR⁹—,        —A¹—A²—X¹—, —A¹—A¹—A²—X¹—, —O—A²—N(R⁹)—A²—, —CR⁷═CR⁷—A²—X¹—,        —C═C—A²—X —, —N═CR⁸)—A²—X¹—, —C(R⁸)═N—N C(R⁸)—, —C(R⁸)═N—N(R⁹)—,        —(CH₂)₂—O—N═CR⁸)— or —X—A²—N(R⁹)—    -   where    -   n is 0, 1 or 2,    -   k is 1 to 9,    -   A¹ is —CHR⁷—,    -   A² is —C(═X)—,    -   A³ is —C(R⁸)═N—O—,    -   A⁴ is —O—N═C(R⁸)—,    -   X is O or S,    -   X¹ is O, S, NR⁹ or a direct bond,    -   X² is O, NR⁹ or a direct bond,    -   X³ is hydrogen, —C(═O)—, —SO₂— or a direct bond,    -   R⁷, which may be the same or different to any other R⁷, is        alkyl, cycloalkyl or phenyl, each of which may be substituted;        or is hydrogen, halogen, cyano or acyl;    -   R⁸, which may be the same or different to any other R⁸, is        alkyl, alkenyl, alkynyl, alkoxy, alkylthio, carbo- or        heterocyclyl, each of which may be substituted; or is hydrogen:

R⁹, which may be the same or different to any other R⁹, is optionallysubstituted alkyl, optionally substituted carbo- or heterocyclyl,hydrogen or acyl; or two R⁹ groups on A, together with the connectingatoms, form a 5 to 7 membered ring;

-   -   where the moiety depicted on the right side of linkage A is        attached to R⁶;    -   or —A—R⁶ and R⁵ together with benzene ring M form an optionally        substituted fused ring system.

Preferably R¹ is alkyl, alkenyl or alkynyl, each of which may besubstituted by alkoxy, haloalkoxy, alkylthio, halogen or optionallysubstituted phenyl (preferably phenyl optionally substituted by alkyl,haloalkyl, alkoxy, haloalkoxy or alkylthio, each containing 1 to 5carbon atoms, or halogen), or is hydrogen. R¹ is especially C₁-C₁₀ alkyl(e.g. methyl) or hydrogen.

Preferably R² and R³, which may be the same or different, are alkyl,alkenyl or alkynyl, each of which may be substituted by alkoxy,haloalkoxy, alkylthio, halogen or optionally substituted phenyl(preferably phenyl, optionally substituted by alkyl, haloalkyl, alkoxy,haloalkoxy or alkylthio, each containing 1 to 5 carbon atoms, or byhalogen), or is hydrogen, alkoxy, alkoxyalkoxy, benzyloxy, cyano oralkylcarbonyl. R² and R³, which may be the same or different, areespecially C₁-C₁₀alkyl (e.g. methyl or ethyl) or hydrogen.

Preferably R⁴ is alkyl, alkenyl, or alkynyl, each of which may besubstituted by alkoxy, haloalkoxy, alkylthio, halogen or optionallysubstituted phenyl (preferably phenyl optionally substituted by alkyl,haloalkyl, alkoxy, haloalkoxy or alkylthio, each containing 1 to 5carbon atoms, or halogen); or is hydroxy; halogen; cyano; acyl(preferably —C(═O)R^(c), —C(═S)R^(c) or —S(O)_(p)R^(c), where R^(c) isalkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, amino, monoalkylamino,dialkylamino or phenyl optionally substituted by alkyl, haloalkyl,alkoxy, haloalkoxy or alkylthio); alkoxy; haloalkoxy; or alkylthio. R⁴is especially C₁-C₁₀ alkyl (e.g. methyl or ethyl) or halogen.

Preferably m is 0 or 1, especially 1.

When present, R⁵ is preferably a group defined for preferred R⁴ above.R⁵ is especially C₁-C₁₀ alkyl or halogen.

When present, the group R⁵ is preferably attached at the 5 position ofring M.

Preferably A is a direct bond, —O—, —S(O)_(n)A¹—, —O(A¹)_(k),—S(O)_(n)—, —NR⁹A²—, —A²—, —OA²—, —OA²—A¹—, —NR⁹—or—O(A¹)_(k)O—Particularly A is a direct bond, —O—, —S—, —NR⁹—, —CHR⁷—or—O—CHR⁷—. Especially A is a direct bond or —O—. When present, R⁹ isalkyl, alkenyl, or alkynyl, each of which may be substituted by alkoxy,haloalkoxy, alkylthio, halogen or optionally substituted phenyl(preferably phenyl optionally substituted by alkyl, haloalkyl, alkoxy,haloalkoxy or alkylthio, each containing 1 to 5 carbon atoms, orhalogen); or is hydrogen (R⁹ is especially C₁-C₁₀ alkyl or hydrogen).When present, R⁷ is alkyl, alkenyl, or alkynyl, each of which may besubstituted by alkoxy, haloalkoxy, alkylthio, halogen or optionallysubstituted phenyl (preferably phenyl optionally substituted by alkyl,haloalkyl, alkoxy, haloalkoxy or alkylthio, each containing 1 to 5carbon atoms, or by halogen); or is hydroxy; halogen; cyano: acyl;alkoxy; haloalkoxy; alkylthio; or hydrogen (R⁷ is especially C₁-C₁₀alkyl or hydrogen).

Preferably A is attached to the 4 position of benzene ring M.

Preferably R⁶ is optionally substituted phenyl or optionally substitutedaromatic heterocyclyl [preferably thiazolyl, isothiazolyl, thiadiazolyl[particularly 1,2,4-thiadiazolyl), pyridyl or pyrimidinyl].

When substituted, R⁶ may be substituted by one or more substituents,which may be the same or different, and may be selected from thepreferred list: alkyl, alkenyl, alkynyl, carbo- or heterocycyl, each ofwhich may be substituted;

-   -   hydroxy; mercapto; azido; nitro; halogen; cyano: acyl;        optionally substituted amino; cyanato; thiocyanato; —SF₅;        —OR^(a); —SR^(a) and —Si(R^(a))₃, where R^(a) is alkyl, alkenyl,        alkynyl, carbocyclyl or heterocyclyl, each of which may be        substituted.

A preferred list of substituents on R⁶ is: hydroxy; halogen; cyano; acyl(preferably —C(═O)R^(c), —C(═S)R^(c) or —S(O)_(p)R^(c), where R^(c) isalkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, amino, monalkylamino,dialkylamino or phenyl optionally substituted by alkyl, haloalkyl,alkoxy, haloalkoxy or alkylthio); amino: alkylamino; dialkylamino;alkyl; haloalkyl; R^(a)O-alkyl; acyloxyalkyl; cyano-oxyalkyl; alkoxy;haloalkoxy; alkylthio; carbocyclyl (preferably cyclohexyl orcyclopentyl) optionally substituted by alkyl, haloalkyl, alkoxy,haloalkoxy or alkylthio; and benzyl optionally substituted by alkyl,haloalkyl, alkoxy, haloalkoxy or alkylthio.

A particularly preferred list of substituents on R⁶ is: cyclopentyl,cyclohexyl or benzyl, optionally substituted by alkyl, haloalkyl,alkoxy, haloalkoxy, or alkylthio; or is halogen; alkyl; haloalkyl;alkoxyalkyl; hydroxyalkyl; alkoxy; or alkylthio.

In a preferred embodiment, the invention provides the use of a compoundof general formula I and salts thereof as fungicides wherein:

-   -   R¹ is alkyl, alkenyl or alkynyl, each of which may-be        substituted by alkoxy, haloalkoxy, alkylthio, halogen or phenyl        optionally substituted by alkyl, haloalkyl, alkoxy, haloalkoxy,        alkylthio or halogen; or is hydrogen;    -   R² and R³, which may be the same or different, are as defined        for R¹ in this embodiment, or are alkoxy, alkoxyalkoxy,        benzyloxy, cyano or alkylcarbonyl;    -   R⁴ is alkyl, alkenyl or alkynyl, each of which may be        substituted by alkoxy, haloalkoxy, alkylthio, halogen or phenyl        optionally substituted by alkyl, haloalkyl, alkoxy, haloalkoxy,        alkylthio or halogen; or is hydroxy; halogen; cyano; acyl        (preferably —C(═O)RC, —C(═S)Rc or —S(O)_(p)R^(c), where R^(c) is        alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, amino,        monoalkylamino, dialkylamino or phenyl optionally substituted by        alkyl, haloalkyl, alkoxy, haloalkoxy or alkylthio);    -   m is 0 or 1;    -   when present, R⁵ is a group defined for R⁴ in this embodiment;    -   A is a direct bond, —O—, —S—, —NR⁹—, —CHR⁷—or —O—CHR⁷—, wherein        when present, R⁹ is alkyl, alkenyl, or alkynyl, each of which        may be substituted by alkoxy, haloalkoxy, alkylthio, halogen or        phenyl optionally substituted by alkyl, haloalkyl, alkoxy,        haloalkoxy, alkylthio, or halogen; or is hydrogen; and R⁷ is a        group defined for R⁹ in this embodiment, or is hydroxy; halogen;        cyano; acyl; alkoxy; haloalkoxy or alkylthio;    -   A is attached to the 4 position of benzene ring M; and    -   R⁶ is phenyl or aromatic heterocyclyl, optionally substituted by        one or more substituents, which may be the same or different,        and may be selected from the list: hydroxy; halogen; cyano; acyl        (preferably —C(═O)R^(c), —C(═S)R^(c) or —S(O)_(p)R^(c), where        R^(c) is alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, amino,        monoalkylamino, dialkylamino or phenyl optionally substituted by        alkyl, haloalkyl, alkoxy, haloalkoxy or alkylthio): amino;        alkylamino; dialkylamino; alkyl; haloalkyl; R^(a)O-alkyl;        acyloxyalkyl; cyano-oxyalkyl; alkoxy; haloalkoxy; alkylthio;        carbocyclyl (preferably cyclohexyl or cyclopentyl) optionally        substituted by alkyl, haloalkyl, alkoxy, haloalkoxy or        alkylthio; and benzyl optionally substituted by alkyl,        haloalkyl, alkoxy, haloalkoxy or alkylthio.

Most compounds of general formula I are novel. Therefore according to asecond aspect, the invention provides compounds of formula I wherein

-   -   R¹ is alkyl, alkenyl, alkynyl, carbocyclyl or heterocyclyl, each        of which may be substituted, or is hydrogen;    -   R² and R³, which may be the same or different, are any group        defined for R¹, or together with the nitrogen to which they are        attached may form a ring, which may be substituted;    -   R⁴ is alkyl, alkenyl, alkynyl, carbocyclyl or heterocyclyl, each        of which may be substituted;    -   m is 1;    -   R⁵ is any group defined for R⁴ attached to the 5-position of the        benzene ring M;    -   R⁶ is optionally substituted carbo- or heterocyclyl; and    -   A is a direct bond; —O—; —S—; —NR⁹—, where R⁹ is alkyl, alkenyl,        or alkynyl, each of which may be substituted by alkoxy,        haloalkoxy, alkylthio, halogen or optionally substituted phenyl;        —CHR¹⁷— or —O—CHR⁷—, where R⁷ is alkyl, alkenyl, or alkynyl,        which may be substituted by alkoxy, haloalkoxy, alkylthio,        halogen or phenyl optionally substituted by alkyl, haloalkyl,        alkoxy, haloalkoxy or alkylthio; or is hydroxy; halogen; cyano;        acyl; alkoxy; haloalkoxy; or alkylthio;    -   where —A—R⁶ is in the 4-position of the benzene ring M and the        moiety depicted on the right side of linkage A is attached to        R⁶;    -   or —A—R⁶ and R⁵ together with benzene ring M form an optionally        substituted fused ring system.

Any alkyl group may be straight or branched and is preferably of 1 to 10carbon atoms, especially 1 to 7 and particularly 1 to 5 carbon atoms.

Any alkenyl or alkynyl group may be straight or branched and ispreferably of 2 to 7 carbon atoms and may contain up to 3 double ortriple bonds which may be conjugated, for example vinyl, allyl,butadienyl or propargyl.

Any carbocyclyl group may be saturated, unsaturated or aromatic, andcontain 3 to 8 ring-atoms. Preferred saturated carbocyclyl groups arecyclopropyl, cyclopentyl or cyclohexyl. Preferred unsaturatedcarbocyclyl groups contain up to 3 double bonds. A preferred aromaticcarbocyclyl group is phenyl. The term carbocylic should be similarlyconstrued. In addition, the term carbocyclyl includes any fusedcombination of carbocyclyl groups, for example naphthyl, phenanthryl,indanyl and indenyl.

Any heterocyclyl group may be saturated, unsaturated or aromatic, andcontain 5 to 7 ring-atoms up to 4 of which may be hetero-atoms such asnitrogen, oxygen and sulfur. Examples of heterocyclyl groups are furyl,thienyl, pyrrolyl, pyrrolinyl, pyrrolidinyl, imidazolyl, dioxolanyl,oxazolyl, thiazolyl, imidazolyl, imidazolinyl, imidazolidinyl,pyrazolyl, pyrazolinyl, pyrazolidinyl, isoxazolyl, isothiazolyl,oxadiazolyl, triazolyl, thiadiazolyl, pyranyl, pyridyl, piperidinyl,dioxanyl, morpholino, dithianyl, thiomorpholino, pyridazinyl,pyrimidinyl, pyrazinyl, piperazinyl, sulfolanyl, tetrazolyl, triazinyl,azepinyl, oxazepinyl, thiazepinyl, diazepinyl and thiazolinyl. Inaddition, the term heterocyclyl includes fused heterocyclyl groups, forexample benzimidazolyl, benzoxazolyl, imidazopyridinyl, benzoxazinyl,benzothiazinyl, oxazolopyridinyl, benzofuranyl, quinolinyl,quinazolinyl, quinoxalinyl, dihydroquinazolinyl, benzothiazolyl,phthalimido, benzofuranyl, benzodiazepinyl, indolyl and isoindolyl. Theterm heterocyclic should be similarly construed.

Any alkyl, alkenyl, alkynyl, carbocyclyl or heterocyclyl group, whensubstituted, may be substituted by one or more substituents, which maybe the same or different, and may be selected from the list: hydroxy;mercapto; azido; nitro; halogen; cyano; acyl; optionally substitutedamino: optionally substituted carbocyclyl; optionally substitutedheterocyclyl; cyanato; thiocyanato; —SF₅; —OR^(a); —SR^(a) and—Si(R^(a))₃, where R^(a) is alkyl, alkenyl, alkynyl, carbocyclyl orheterocyclyl, each of which may be substituted. In the case of anycarbocyclyl or heterocyclyl group the list includes additionally: alkyl,alkenyl and alkynyl, each of which may be substituted. Preferredsubstituents on any alkyl, alkenyl or alkynyl group are alkoxy,haloalkoxy or alkylthio, each containing 1 to 5 carbon atoms; halogen;or optionally substituted phenyl. Preferred substituents on anycarbocyclyl or heterocyclyl group are alkyl, haloalkyl, alkoxy,haloalkoxy or alkylthio, each containing 1 to 5 carbon atoms; halogen;or optionally substituted phenyl.

In the case of any alkyl group or any unsaturated ring-carbon in anycarbocyclyl or heterocyclyl group the list includes a divalent groupsuch as oxo or imino, which may be substituted by optionally substitutedamino, R^(a) or —OR^(a) (where R^(a) is as defined above). Preferredgroups are oxo, imino, alkylimino, oximino, alkyloximino or hydrazono.

Any amino group, when substituted and where appropriate, may besubstituted by one or two substituents which may be the same ordifferent, selected from the list: optionally substituted alkyl,optionally substituted amino, —OR^(a) (where R^(a) is as defined above)and acyl groups. Alternatively two substituents together with thenitrogen to which they are attached may form a heterocyclyl group,preferably a 5 to 7-membered heterocyclyl group, which may besubstituted and may contain other hetero atoms, for example morpholino,thiomorpholino or piperidinyl.

The term acyl includes the residues of sulfur and phosphorus-containingacids as well as carboxylic acids. Typically the residues are covered bythe general formulae —C(═X^(a))R^(b), —S(O)_(p)R^(b) and—P(═X^(a))(OR^(a))(OR^(a)), where appropriate X^(a) is O or S, R^(b) isas defined for R^(a), —OR^(a), —SR^(a), optionally substituted amino oracyl; and p is 1 or 2. Preferred groups are —C(═O)Rc, —C(═S)Rc, and—S(O)_(p)Rc where RC is alkyl, C₁ to C₅ alkoxy, C₁ to C₅ alkylthio,phenyl, heterocyclyl or amino, each of which may be substituted.

Complexes of compounds of the invention are usually formed from a saltof formula MAn₂, in which M is a divalent metal cation, e.g. copper,manganese, cobalt, nickel, iron or zinc and An is an anion, e.g.chloride, nitrate or sulfate.

In cases where the compounds of the invention exist as the E and Zisomers, the invention includes individual isomers as well as mixturesthereof.

In cases where compounds of the invention exist as tautomeric isomers,the invention includes individual tautomers as well as mixtures thereof.

In cases where the compounds of the invention exist as optical isomers,the invention includes individual isomers as well as mixtures thereof.

The compounds of the invention have activity as fungicides, especiallyagainst fungal diseases of plants, e.g. mildews and particularly cerealpowdery mildew (Erysiphe graminis) and vine downy mildew (Plasmoparaviticola), rice blast (Pyricularia oryzae), cereal eyespot(Pseudocercosporella herpotrichoides), rice sheath blight (Pelliculariasasakii), grey mould (Botrytis cinerea), damping off (Rhizoctoniasolani), wheat brown rust (Puccinia recondita), late tomato or potatoblight (Phytophthora infestans), apple scab (Venturia inaequalis), andglume blotch (Leptosphaeria noaorum). Other fungi against which thecompounds may be active include other powdery mildews, other rusts, andother general pathogens of Deuteromycete, Ascomycete, Phycomycete andBasidomycete origin.

The invention thus also provides a method of combating fungi at a locusinfested or liable to be infested therewith, which comprises applying tothe locus a compound of formula I.

The invention also provides an agricultural composition comprising acompound of formula I in admixture with an agriculturally acceptablediluent or carrier.

The composition of the invention may of course include more than onecompound of the invention.

In addition, the composition can comprise one or more additional activeingredients, for example compounds known to possess plant-growthregulant, herbicidal, fungicidal, insecticidal, acaricidal,antimicrobial or antibacterial properties. Alternatively the compound ofthe invention can be used in sequence with the other active ingredient.

The diluent or carrier in the composition of the invention can be asolid or a liquid optionally in association with a surface-active agent,for example a dispersing agent, emulsifying agent or wetting agent.Suitable surface-active agents include anionic compounds such as acarboxylate, for example a metal carboxylate of a long chain fatty acid;an N-acylsarcosinate: mono- or di-esters of phosphoric acid with fattyalcohol ethoxylates or alkyl phenol ethoxylates or salts of such esters;fatty alcohol sulfates such as sodium dodecyl sulfate, sodium octadecylsulfate or sodium cetyl sulfate; ethoxylated fatty alcohol sulfates;ethoxylated alkylphenol sulfates; lignin sulfonates; petroleumsulfonates; alkyl-aryl sulfonates such as alkyl-benzene sulfonates orlower alkylnaphthalene sulfonates, e.g. butyl-naphthalene sulfonate;salts of sulfonated naphthalene-formaldehyde condensates; salts ofsulfonated phenol-formaldehyde condensates; or more complex sulfonatessuch as the amide sulfonates, e.g. the sulfonated condensation productof oleic acid and N-methyl taurine; the dialkyl sulfosuccinates, e.g.the sodium sulfonate of dioctyl succinate; acid derivatives of alkylglycosides and alkylpolyglycosides materials and their metal salts, e.g.alkyl polyglycoside citrate or tartrate materials; or mono-, di- andtri-alkyl esters of citric acid and their metal salts.

Nonionic agents include condensation products of fatty acid esters,fatty alcohols, fatty acid amides or fatty-alkyl- or alkenyl-substitutedphenols with ethylene and/or propylene oxide; fatty esters of polyhydricalcohol ethers, e.g. sorbitan fatty acid esters; condensation productsof such esters with ethylene oxide, e.g. polyoxyethylene sorbitan fattyacid esters; alkyl glycosides, alkyl polyglycoside materials; blockcopolymers of ethylene oxide and propylene oxide; acetylenic glycolssuch as 2,4,7,9-tetramethyl-5-decyne-4,7-diol, ethoxylated acetylenicglycols; acrylic based graft copolymers; alkoxylated siloxanesurfactants; or imidazoline type surfactants, e.g.1-hydroxyethyl-2-alkylimidazoline.

Examples of a cationic surface-active agent include, for instance, analiphatic mono-, di-, or polyamine as an acetate, naphthenate or oleate;an oxygen-containing amine such as an amine oxide, polyoxyethylenealkylamine or polyoxypropylene alkylamine; an amide-linked amineprepared by the condensation of a carboxylic acid with a di- orpolyamine; or a quaternary ammonium salt.

The compositions of the invention can take any form known in the art forthe formulation of agrochemicals, for example, a solution, an aerosol, adispersion, an aqueous emulsion, a microemulsion, a dispersibleconcentrate, a dusting powder, a seed dressing, a fumigant, a smoke, adispersible powder, an emulsifiable concentrate, granules or animpregnated strip. Moreover it can be in a suitable form for directapplication or as a concentrate or primary composition which requiresdilution with a suitable quantity of water or other diluent beforeapplication.

A dispersible concentrate comprises a compound of the inventiondissolved in one or more water miscible or semi-water miscible solventstogether with one or more surface active and/or polymeric material.Addition of the formulation to water results in the crystalisation ofthe active ingredient, the process being controlled by the surfactantsand/or polymers resulting in a fine dispersion.

A dusting powder comprises a compound of the invention intimately mixedand ground with a solid pulverulent diluent, for example, kaolin.

An emulsifiable concentrate comprises a compound of the inventiondissolved in a water-immiscible solvent which forms an emulsion ormicroemulsion on addition to water in the presence of an emulsifyingagent.

A granular solid comprises a compound of the invention associated withsimilar diluents to those that may be employed in dusting powders, butthe mixture is granulated by known methods. Alternatively it comprisesthe active ingredient absorbed or coated on a pre-formed granularcarrier, for example, Fuller's earth, attapulgite, silica or limestonegrit.

Wettable powders, granules or grains usually comprise the activeingredient in admixture with suitable surfactants and an inert powderdiluent such as clay or diatomaceous earth.

Another suitable concentrate is a flowable suspension concentrate whichis formed by grinding the compound with water or other liquid,surfactants and a suspending agent.

The concentration of the active ingredient in the composition of thepresent invention, as applied to plants is preferably within the rangeof 0.0001 to 1.0 percent by weight, especially 0.0001 to 0.01 percent byweight. In a primary composition, the amount of active ingredient canvary widely and can be, for example, from 5 to 95 percent by weight ofthe composition.

In use a compound of the invention is generally applied to seeds, plantsor their habitat. Thus, the compound can be applied directly to the soilbefore, at or after drilling so that the presence of active compound inthe soil can control the growth of fungi which may attack seeds. Whenthe soil is treated directly the active compound can be applied in anymanner which allows it to be intimately mixed with the soil such as byspraying, by broadcasting a solid form of granules, or by applying theactive ingredient at the same time as drilling by inserting it in thesame drill as the seeds. A suitable application rate is within the rangeof from 5 to 1000 g per hectare, more preferably from 10 to 500 g perhectare.

Alternatively the active compound can be applied directly to the plantby, for example, spraying or dusting either at the time when the fungushas begun to appear on the plant or before the appearance of fungus as aprotective measure. In both such cases the preferred mode of applicationis by foliar spraying. It is generally important to obtain good controlof fungi in the early stages of plant growth, as this is the time whenthe plant can be most severely damaged. The spray or dust canconveniently contain a pre- or post-emergence herbicide if this isthought necessary. Sometimes, it is practicable to treat the roots,bulbs, tubers or other vegetative propagule of a plant before or duringplanting, for example, by dipping the roots in a suitable liquid orsolid composition. When the active compound is applied directly to theplant a suitable rate of application is from 0.025 to 5 kg per hectare,preferably from 0.05 to 1 kg per hectare.

In addition, the compounds of the invention can be applied to harvestedfruits, vegetables or seeds to prevent infection during storage.

In addition, the compounds of the invention can be applied to plants orparts thereof which have been genetically modified to exhibit a traitsuch as fungal and/or herbicidal resistance.

In addition the compounds of the invention can be used to treat fungalinfestations in timber and in public health applications. Also thecompounds of the invention can be used to treat fungal infestations indomestic and farm animals.

Compounds of the invention may be prepared, in known manner, in avariety of ways.

Compounds of general formula I may be prepared from compounds of generalformula II according to Scheme 1. The following reaction conditions maybe used to effect conversion:

-   -   a) reaction with R²R³NC(R¹)(OR)₂, where R is a group such as        alkyl;    -   b) reaction with ROC(R¹)═NCN;    -   c) when R¹ is hydrogen, by reaction with H(C═O)NR²R³ in the        presence of POCl₃ or SOCl₂; or    -   d) in two steps by reaction with phosgene to form the isocyanate        and then treatment with R²R³N(C═O)R¹.

In addition, groups R² and R³ in compounds of general formula I can beconverted to other groups defined for R² and R³, by treatment with anappropriate amine or by acylation or alkylation when R² or R³ ishydrogen.

Compounds of general formula II may be prepared by reduction of thenitro group in compounds of formula III according to reaction scheme 2.Preferred reaction conditions comprise reaction with stannous chloridein concentrated hydrochloric acid.

Compounds of formula IIa, i.e. compounds of general formula II where Ais a direct bond, may be prepared according to reaction scheme 3, whereX^(V) is a leaving group.

Compounds of formula IIb, i.e. compounds of general formula II where R⁴is halogen, may be prepared according to scheme 4 where XT representshalogen. When R⁴ is bromine preferred reaction conditions comprisestirring with bromine in a suitable solvent.

Compounds of formula IIc, i.e. compounds of general formula II where Ais NHC(═O)—; compounds of formula IId, i.e. compounds of formula IIwhere A is a direct bond and R⁶ is optionally substituted phthalimido,where the curved line connecting the 3 and 4 positions of thephthalimido group represents the optionally substituted carbocyclicring; and compounds of formula IIe, i.e. compounds of general formula IIwhere A is a direct bond and R⁶ is pyrrolyl, optionally substituted atthe 2 and 5 positions by one or more groups R which may be the same ordifferent; may be prepared from compounds of formula IV according tomethodology shown in reaction scheme 5. For certain compounds of formulaIV, protection/deprotection of the amino group ortho to R⁴ may berequired to improve yields.

Compounds of formula IIIa, i.e. compounds of general formula III where Ais a group A^(Z), may be prepared by reacting compounds of formula Vwith compounds of formula VI according to reaction scheme 6. AZ is agroup which, in compound V, forms an anion under basic conditions. A^(Z)is alternatively a basic primary or secondary nitrogen atom. X^(Z) is aleaving group, preferably halogen. When A^(Z) is oxygen, preferredreaction conditions comprise treating V with sodium hydride followed byaddition of VI. When A^(Z) is sulfur preferred reaction conditionscomprise reacting V with VI in the presence of a tertiary amine basesuch as ethyldiisopropylamine. When A^(Z) is —CHR⁷—, preferred reactionconditions comprise treating V with potassium tert-butoxide indimethylformamide at low temperature. When A^(Z) is a basic nitrogenatom, no base is required.

Compounds of formula IIIb, i.e. compounds of general formula III where Ais a group A^(W), may be prepared by reacting compounds of formula VIIwith compounds of formula VIII according to reaction scheme 7. A^(W) isa group which, in compound VII, forms an anion under basic conditions.X^(W) is a leaving group, preferably halogen. Preferred basic conditionscomprise reaction of VII with potassium carbonate or sodium hydridefollowed by addition of VII.

Compounds of formula IIIc, i.e. compounds of general formula III where Ais O, may be prepared by reacting compounds of formula IX with boronicacids of formula X according to Scheme 8. Preferred reaction conditionscomprise reaction with copper acetate and triethylamine.

Compounds of formula IIId, i.e. compounds of formula III where A is adirect bond may be prepared according to reaction scheme 9 fromcompounds of formula XI where X^(Z) is a leaving group, preferablyhalogen.

Compounds of formula III where A is a direct bond and R⁶ is aheterocyclyl can be prepared using a variety of methods known to askilled chemist (for example see “Comprehensive Heterocyclic Chemistry”,Vols 1-7, A. R. Katritzky and C. W. Rees). By way of example, routes tocompounds of formula III containing a 1,2,4-oxadiazol-3-yl group(compound IIIe) and a 1,3,4-oxadiazol-2-yl group (compound IIIf) areshown in schemes 10 and 11.

Alternatively, using similar chemistry to that described above,compounds of formula I can be prepared by introducing R⁶ after formationof the amidine moiety.

In particular, we have found that treating compounds of formula XII tothe reaction conditions of Scheme 7 gives compounds of formula Ia, i.e.compounds of general formula I where A is oxygen, in particularly highyield (see Scheme 12). Compounds of formula XII may be prepared bymethods similar to those described in Tetrahedron Letters, 38 (31)5403-5406.

Some compounds of general formula XII are novel, therefore according toa third aspect the invention provides compounds of general formula XIIa,

where

-   -   R¹ is alkyl, alkenyl, alkynyl, carbocyclyl or heterocyclyl, each        of which may be substituted, or is hydrogen;    -   R² and R³, which may be the same or different, are any group        defined for R¹; cyano; acyl; —OR^(a) or —SR^(a), where R^(a) is        alkyl, alkenyl, alkynyl, carbocyclyl or heterocyclyl, each of        which may be substituted; or R² and R³, or R² and R¹, together        with their interconnecting atoms may form a ring, which may be        substituted;    -   R⁴ is alkyl, alkenyl, alkynyl, carbocyclyl or heterocyclyl, each        of which may be substituted; and    -   R⁵ is any group defined for R⁴;        with the proviso that R⁵ is not tert-butyl.

Other methods will be apparent to the chemist skilled in the art, aswill be methods for preparing starting materials and intermediates.

In addition, compounds of the invention may be prepared usingcombinatorial chemistry methodology.

The invention is illustrated in the following Examples. Structures ofisolated, novel compounds were confirmed by N.M.R. and/or otherappropriate analyses. Proton N.M.R. spectra (¹H N.M.R.) were determinedin deuterochloroform and chemical shifts (δ) are quoted in parts permillion downfield of tetramethylsilane.

EXAMPLE 1N,N-Dimethyl-N′-[4-(3-trifluoromethylbenzylthio)-2,5-xylyl]formamidine

(Compound 3)

The product from stage b) (1.0 g) and N,N-dimethylformamidedimethylacetal (1.0 ml) were heated at 100° C. for 4 hours. On coolingthe mixture was purified by silica gel chromatography eluting withdiethyl ether to give the title compound, ¹H N.M.R. δ(ppm) 2.15 (s, 3H,ArCH₃), 2.20 (s, 3H, ArCH₃), 3.00 (s, 6H, N(CH₃)₂), 3.95 (s, 2H, SCH₂).

Preparation of Starting Materials

a) 2-Nitro-5-(3-trifluoromethylbenzylthio)-p-xylene

A mixture of 3-trifluoromethylbenzyl mercaptan (3.42 g),diisopropylethylamine (2.3 g) and 3-chloro-6-nitro-p-xylene (3.0 g) indry N-methylpyrrolidinone (20 ml) was heated at 130° C. for 6 hours. Oncooling, the mixture was poured into ice-water and the resulting mixturewas filtered to give a solid which was washed with ice-water and thenair dried. The solid was purified by silica gel chromatography elutingwith light petroleum (60-80° C.)/ethyl acetate (9:1) to give the titleproduct as a solid, m.p. 85-7° C.

b) 4-(3-Trifluoromethylbenzylthio)-2,5-xylidine

To a stirred mixture of stannous chloride (10.8 g) in concentratedhydrochloric acid (24 ml) and ethanol (50 ml) was added the product fromstage a) above (2.46 g) and the mixture was heated at 75° C. for 2hours. On cooling potassium hydroxide solution was added slowly withcooling. The mixture was extracted with diethyl ether (x3) and thecombined extracts were washed with brine, dried (MgSO₄), filtered andevaporated to dryness to give a crude residue which was purified bysilica gel chromatography eluting with light petroleum (b.p. 60-80°C.)/ethyl acetate (3:1) to give the title product, m.p. 58-60° C.

EXAMPLE 2N,N-Diethyl-N′-[4-(3-trifluoromethylphenoxy)-2,5-xylyl]formamidine

(Compound 37)

Under an atmosphere of nitrogen, phosphorous oxychloride (2.18 g) in drydiethyl ether (3 ml) was added dropwise to a stirred solution ofN,N-diethylformamide (1.43 g) in dry diethyl ether (3 ml) and stirringcontinued for 20 minutes. Stirring was stopped and the mixture allowedto form two layers. The upper ether layer was removed by decanting, andthe lower layer was washed with diethyl ether (x3). The product fromstage b) (2 g) in dry diethyl ether (4 ml) was then added dropwise.After addition the mixture was stirred vigorously for 1 hour at roomtemperature. The upper ether layer was removed by decanting and thelower layer was washed with ether (x2). The lower layer was poured intowater and the mixture adjusted to pH 9 with sodium carbonate solution.The mixture was extracted with diethyl ether (x3) and the combinedextracts were dried (MgSO₄), filtered and evaporated to dryness to givea crude oil which was purified by silica gel chromatography eluting withdiethyl ether to give the title compound, 1H N.M.R. δ(ppm) 1.20 (t, 6H,CH₂CH₃), 2.10 (s, 3H, ArCH₃), 2.20 (s, 3H, ArCH₃), 3.30-3.50 (br, 4H,CH₂CH₃).

Preparation of Starting Materials

a) 2-Nitro-5-(3-trifluoromethylphenoxy)-p-xylene

To a suspension of sodium hydride (0.4 g of 60% in oil) in dryN-methylpyrrolidinone (10 ml) was slowly added 3-trifluoromethylphenol(1.62 g). When effervescence had ceased, 3-chloro-6-nitro-p-xylene (1.85g) was added and the mixture stirred at 120-40° C. for 5 hours. Oncooling, the mixture was poured into water and the mixture extractedwith diethyl ether (x3). The combined ether extracts were dried (MgSO₄),filtered and evaporated to give the title compound as a solid, m.p.68-71° C.

b) 4-(3-Trifluoromethylphenoxy)-2,5-xylidine

This compound was prepared in similar fashion to the product fromExample 1, stage b).

EXAMPLE 3N-Ethyl-N-methyl-N′-[4-(3-trifluoromethylphenoxy)-2,5-xylyl]formamidine

(Compound 45)

A mixture of the product from Example 4 (1 g) and methylethylamine(0.885 g) in acetonitrile (20 ml) was stirred at room temperature for1.5 hours. The solvent was removed in vacuo and water added. The mixturewas extracted with diethyl ether (x3) and the combined ether extractsdried (MgSO₄), filtered and evaporated to dryness. The crude residue waspurified by silica gel chromatography eluting with ethyl acetate/lightpetroleum (b.p. 40-60° C.) (4:6) to give the title compound, 1H N.M.R.δ(ppm) 1.20 (t, 3H, CH₂CH₃), 2.10 (s, 3H, ArCH₃), 2.20 (s, 3H, ArCH₃),3.00 (s, 3H, NCH₃), 3.40 (br, 2H, NCH₂).

EXAMPLE 4 N-Cyano-N′-[4-(3-trifluoromethylphenoxy)-2,5-xylyl]formamidine

(Compound 44)

To a solution of the product from Example 2 stage b) (2 g) in ethanol (5ml) was added dropwise ethyl cyanoimidate (0.7 g) at room temperatureand stirring continued for 2 hours at room temperature. The ethanol wasremoved in vacuo to give a crude residue which was purified bytrituration with light petroleum (b.p. 40-60° C.) followed by silica gelchromatography eluting with ethyl acetate/light petroleum (b.p. 40-60°C.) (4:6) to give the title product, m.p. 138-40° C.

EXAMPLE 5N,N-Dimethyl-N′-[4-(3-phenyl-1,2,4-thiadiazol-5-yloxy)-2,5-xylyl]formamidine

(Compound 48)

To a suspension of the starting material (see below) (0.57 g) indimethylformamide (10 ml) was added potassium carbonate (0.62 g) and thesolution stirred at room temperature for 40 minutes.5-Bromo-3-phenyl-1,2,4-thiadiazole (0.72 g) was added and the mixturestirred at 60° C. for 3 hours. On cooling the mixture was poured intowater (150 ml) and extracted with diethyl ether (3×70 ml). The combinedether extracts were washed with water (20 ml), dried (MgSO₄), filteredand evaporated to dryness to give a crude solid which was purified bysilica gel chromatography eluting with diethyl ether to give the titlecompound as a solid, m.p. 100-5° C.

Preparation of Starting Materials

N,N-Dimethyl-N′-{4-hydroxy-2,5-xylyl}formamidine

This compound was prepared from 4-amino-2,5-dimethylphenol in similarfashion to Examples 1, 2 or 3, m.p. 212° C.

EXAMPLE 6N,N-Dimethyl-N′-[4-(3-trifluoromethylphenoxy)-2,6-xylyl]formamidine

(Compound 20)

This compound was prepared from the product of stage b) below anddimethylformamide dimethylacetal according to the method of Example 1,¹H N.M.R. δ(ppm) 2.15 (s, 6H, ArCH₃), 3.00 (s, 6H, N(CH₃)₂).

Preparation of Starting Materials

a) 2-Nitro-5-(3-trifluoromethylphenoxy)-m-xylene

A mixture of 3,5-dimethyl-4-nitrophenol (1.67 g),3-trifluoromethylbenzene boronic acid (3.8 g), copper (1 acetate (1.82g) and triethylamine (2.02 g) in dichloromethane (50 ml) was stirred atroom temperature for 48 hours. The mixture was evaporated to dryness andpurified by silica gel chromatography eluting with light petroleum (b.p.60-80° C.)/ethyl acetate (19:1) to give the title product as an oil.

b) 4-(3-Trifluoromethylphenoxy)-2,6-xylidine

This compound was prepared from the product of stage a) above accordingto the method of Example 1, stage b).

EXAMPLE 7N,N-Dimethyl-N′-16-bromo-4-(3-trifluoromethylphenoxy)-2.5-xylyl]formamidine

(Compound 12)

The title product was prepared from the product of stage c) below anddimethylformamide dimethylacetal according to Example 1, ¹H N.M.R.δ(ppm) 2.17 (s, 3H, ArCH₃), 2.22 (s, 3H, ArCH₃), 3.05 (s, 6H, N(CH₃)₂).

Preparation of Starting Materials

a) 2-Nitro-5-(3-trifluoromethylphenoxy)-α-xylene

The title product was prepared from 2,5-dimethyl-4-nitrophenol and3-trifluoromethylbenzene boronic acid according to Example 6, stage a).

b) 4-(3-Trifluoromethylphenoxy)-2,5-xylidine

The title product was prepared from the product of stage a) according toExample 1, stage b).

c) 6-Bromo-4-(3-trifluoromethylphenoxy)-2,5-xylidine

To a stirred solution of the product from stage b) above (1.12 g) indichloromethane (20 ml) was added dropwise bromine (0.64 g) indichloromethane (5 ml) at 0° C. The mixture was washed with sodiumbicarbonate solution, dried (MgSO₄), filtered and evaporated to give acrude oil which was purified by silica gel chromatography eluting withethyl acetate/light petroleum (b.p. 60-80° C.) (1:4) to give the titleproduct.

EXAMPLE 8N,N-Dimethyl-N′-[4-(3-trifluoromethylphenyl)-2,5-xylyl]formamidine

(Compound 53)

The title product was prepared from the product of stage c) below anddimethylformamide dimethylacetal according to Example 1, ¹H N.M.R.δ(ppm) 2.00 (s, 3H, ArCH₃), 2.20 (s, 3H, ArCH₃), 3.00 (s, 6H, (NCH₃)₂).

Preparation of Starting Materials

a) N-(4-Bromo-2,5-xylyl)pivalamide

To a solution of 4-bromo-2,5-xylidine (8 g) in pyridine (60 ml) wasadded pivaloyl chloride (4.7 ml) at room temperature. After 30 minutes,the mixture was poured into dilute hydrochloric acid/ice solution. Theprecipitate was filtered and washed with water to give the titleproduct.

b) N-(4-(3-Trifluoromethylphenyl)-2,5-xylyl)pivalamide

To a solution of the product of stage a) (9.1 g) in dimethoxyethane (14ml) was added triphenylphosphinepalladium (II) chloride (catalyticamount) and stirred for 10 minutes. 3-Trifluoromethyphenylboronic acid(6.03 g), sodium bicarbonate (8.1 g) and water (102 ml) were added andthe mixture heated under reflux for 4 hours. On cooling 1 N sodiumhydroxide solution (94 ml) was added the mixture extracted with ethylacetate. The organic extracts were washed with saturated sodium chloridesolution, dried (MgSO₄) and concentrated to give the title product.

c) 4-(3-Trifluoromethylphenyl)-2,5-xylidine

The product from stage b) (10.4 g) in glacial acetic acid (36 ml) wastreated with hydrochloric acid (24.5 ml of 15% solution) at 70° C. Themixture was stirred for 3 days at 100° C. On cooling, water was addedand the mixture extracted with ethyl acetate. The organic phase waswashed with sodium bicarbonate solution, dried (MgSO₄) and concentratedto give the title product.

EXAMPLE 9N,N-Dimethyl-N′-[4-(3-trifluoromethylbenzyl)-2,5-xylyl]formamidine

(Compound 264)

The title compound was prepared from the product of stage d) below insimilar fashion to Example 1, m.p. 75-7° C.

Preparation of Starting Materials

a) 2-Nitro-5-(α-cyano-3-trifluoromethyl benzyl)-p-xylene

The title product was prepared from 2-chloro-5-nitro-p-xylene and3-trifuoromethylbenzyl cyanide according to the methodology in J. Med.Chem., 40, 3942 (1997).

b) 2-Nitro-(5-(3-trifluoromethylbenzoyl)-p-xylene

Potassium tert-butoxide (1.12 g) was added to a solution of the productfrom stage a) (3.3 g) in dry dimethylformamide (30 ml) at 0° C. andstirred at 0° C. for 5 minutes. Hydrogen peroxide (3.5 ml, 30%) wasadded dropwise and stirring continued for 6 hours at approximately 3° C.The reaction mixture was allowed to stand at room temperature for 2days. The reaction mixture was poured into dilute hydrochloric acid (500ml), and sodium metabisulfite was added. The mixture was extracted withdiethyl ether (2×200 ml), washed with water (2×20 ml), dried (MgSO₄) andconcentrated to give a crude product. Trituration from light petroleum(b.p. 40-60° C.) gave a solid which was recrystallised from diisopropylether to give the title product.

c) 2-Nitro-5-(3-trifluoromethylbenzyl)-p-xylene

To a solution of the product of stage b) (1 g) in dichloromethane (20ml) at 0° C. was added a solution of trifluoromethane sulfonic acid (0.6ml) in dichloromethane (10 ml). Triethylsilane (0.8 ml) indichloromethane (10 ml) was added and stirred at 0° C. for 10 minutes. Afurther portion of trifluoromethane sulfonic acid (0.6 ml) was addedfollowed by a further portion of triethylsilane (0.8 ml). The mixturewas allowed to warm to room temperature and stirred for 1 hour. Themixture was poured into saturated sodium bicarbonate solution (100 ml)and the inorganic solid filtered. The layers were separated and theaqueous layer extracted with dichloromethane (2×50 ml). The combinedorganic layers were evaporated and recrystallised to give a solid, m.p.75-7° C.

d) 4-(3-Trifluoromethylbenzyl)-2,5-xylidine

The title compound was prepared from the product of stage c) accordingto Example 1 stage b).

EXAMPLE 10 N,N-Dimethyl-N′-[4-(4-fluorobenzamido)-2,5-xylyl]formamidine

(Compound 98)

The title compound was prepared from the starting material in similarfashion to Example 1, m.p. 166-8— C.

Preparation of Starting Materials

N-(4-Amino-2,5-xylyl)-4-fluorobenzamide

To a solution of p-xylylenediamine (3.0 g) and ethyldiisopropylamine(3.8 ml) in dichloromethane (300 ml) at 0° C., was added dropwise4-fluorobenzoyl chloride (3.5 g). The mixture was warmed to roomtemperature and stirring continued for 4 hours. Water (200 ml) was addedand the mixture was stirred for 30 minutes. The mixture was filtered,washing through with water and dichloromethane. The organic phase waswashed with water, dried (MgSO₄) and evaporated to give a solid, m.p.174-6° C.

EXAMPLE 11 N,N-Dimethyl-N′-(4-phthalimido-2,5-xylyl)formamidine

(Compound 80)

The title compound was prepared from the starting material in similarfashion to Example 1, m.p. 170-3° C.

Preparation of Starting Materials

N-{4-Amino-2,5-xylyl}phthalimide

To a solution of p-xylylenediamine (1.0 g) in N-methylpyrrolidinone wasadded phthalic anhydride (1.1 g) in N-methylpyrrolidinone (10 ml). Themixture was heated at 150° C. for 4 hours. On cooling, the mixture waspoured into water and then filtered. The cake was washed with water anddried, m.p. 167-9° C.

EXAMPLE 12N,N-Dimethyl-N′-[4-(2,5-dimethyl-1-pyrrolyl)-2,5-xylyl]formamidine

(Compound 79)

The title compound was prepared from stage c) below in similar fashionto Example 1, m.p. 90-1° C.

Preparation of Starting Materials

a) N-(4-Amino-2,5-xylyl)acetamide

To a solution of p-xylenediamine (2.0 g) in dichloromethane (200 ml)maintained below 10° C. was added N,N-diisopropylamine (2.52 ml)followed by the dropwise addition of acetylchloride (1.15 g). Themixture was allowed to attain room temperature and stirred overnight.Water (120 ml) was added and the suspension filtered. The filtered solidwas washed with dichloromethane (2×100 ml) and water (100 ml). Allfiltrates were combined and the organic layer separated. The organiclayer was washed with water, dried (MgSO₄) and evaporated to give thetitle product as a solid, m.p. 133-5° C.

b) N-[4-(2,5-Dimethyl-1-pyrrolyl)-2,5-xylyl]acetamide

The product from stage a) 1.0 g) was added to acetonylacetone (0.7 ml)and the mixture heated at 140° C. for 4 hours. On cooling, the mixturewas dissolved in dichloromethane and the solution filtered through(MgSO₄). Concentration gave a crude product which was purified by silicagel chromatography eluting with diethyl ether, to give the titleproduct.

c) 2,5-Dimethyl-4-(2,5-dimethyl-1-pyrrolyl)aniline

A mixture of the product from stage b) (0.6 g), aqueous sodium hydroxidesolution (10 ml, 10%) and ethanol (30 ml) was heated under reflux for 24hours. On cooling, the mixture was extracted with diethyl ether (x2).The combined diethyl ether extracts were water washed, dried (MgSO₄) andconcentrated to give a crude product. Filtration through silica gave thetitle product.

EXAMPLE 13N,N-Dimethyl-N′-[4-(2-benzo[b]thiophenyl)-2,5-xylyl)formamidine

(Compound 187)

The title compound was prepared from stage b) below in similar fashionto Example 1, m.p. 67-8° C.

Preparation of Starting Materials

a) 2-(4-Nitro-2,5-xylyl)benzo[b]thiophene

A mixture of 2-bromo-5-nitro-p-xylene (200 g),2-benzo[b]thiopheneboronic acid (200 g), (Ph₃P)₄Pd (0.36 g) in toluene(60 ml) and ethanol (22 ml) was heated to reflux overnight. Ethylacetate and water were added and the organic phase was separated. Theorganic phase was washed with water, dried (MgSO₄) and filtered througha pad of silica to give the title product.

b) 2,5-Dimethyl-4-(2-benzo[b]thiophenyl)aniline

The title compound was prepared from the product of stage a) aboveaccording to Example 1 stage b).

EXAMPLE 14N,N-Dimethyl-N′-{4-[5-(4-chlorophenyl)-1,2,4-oxadiazol-3-yl]-2-tolyl}formamidine

(Compound 179)

The title compound was prepared from the product of stage c) belowaccording to Example 1, m.p. 136-7° C.

Preparation of Starting Materials

a) 3-Methyl-4-nitrobenzamide Oxime

To a solution of 3-methyl-4-nitrobenzonitrile (5 g) in ethanol (100 ml)at room temperature was added hydroxylamine hydrochloride (2.25 g)followed by triethylamine (4.5 ml). The mixture was heated under refluxfor 2.5 hours. On cooling the mixture was evaporated to a third of itsoriginal volume and poured on to water (200 ml). The mixture wasfiltered to give the title product as a solid, m.p. 127-9° C.

b) 5-(4-Chlorophenyl)-3-(3-methyl-4-nitrophenyl)-1,2,4-oxadiazole

To a solution of the product from stage a) (1.9 g) and triethylamine(1.62 ml) in dichloromethane 150 ml) at room temperature was added4-chlorobenzoyl chloride (2.05 g). The mixture was stirred at roomtemperature for 2 hours and then washed with water. Toluene (100 ml) wasadded and the mixture was heated under Dean and Stark conditions for 5hours. On cooling the mixture was filtered and concentrated. Triturationwith diisopropylamine and light petroleum (b.p. 40-60° C.) gave thetitle product, m.p. 145-7° C.

c) 4-[5-(4-Chlorophenyl)-1,2,4-oxadiazol-3-yl]-2-methylaniline

The title compound was prepared from the product of stage b) accordingto Example 1 stage b).

EXAMPLE 15N,N-Dimethyl-N′-[4-(5-tert-butyl-1,3,4-oxadiazol-2-yl)-2-methylphenyl]formamidine

(Compound 211)

The title compound was prepared from the product of stage c) belowaccording to Example 1, m.p. 79-80° C.

Preparation of Starting Materials

a) N-(3-Methyl-4-nitrobenzoyl)-N′-pivalolyhydrazine

To a solution of 3-methyl-4-nitrobenzoylhydrazine (3.9 g) indichloromethane (100 ml) was added triethylamine (3.06 ml) followed bypivaloyl chloride (2.6 ml). The mixture was stirred at room temperaturefor 2 hours. The mixture was washed with water, dried (MgSO₄) andconcentrated. Trituration with light petroleum (b.p. 60-80° C.) gave thetitle product, m.p. 125-7° C.

b) 5-tert-Butyl-2-(3-methyl-4-nitrophenyl)-1,3,4-oxadiazole

The product prepared in stage a) (5.0 g) was stirred in toluene (200 ml)and treated with phosphorous pentoxide (10 g). The mixture was heatedunder reflux for 2 hours and then poured onto ice-water. The mixture wasextracted with diethyl ether, the extract dried (MgSO₄) andconcentrated. The residue was purified by silica gel chromatographyeluting with diethyl ether/light petroleum (b.p. 60-80° C.) to give thetitle product, m.p. 123-5° C.

c) 2-(4-Amino-3-methyl)-5-tert-butyl-1,3,4-oxadiazole

The title compound was prepared from the product of stage b) accordingto Example 1 stage b).

EXAMPLE 16

N—Cyano-N-methyl-N′-[4-(4-chloro-3-trifluoromethylphenoxy)-2-xylyl]formamidine

(Compound 373)

The product from stage c) (0.4 g) in tetrahydrofuran (10 ml) was treatedwith sodium hydride (0.05 g). Iodomethane (0.075 ml) was added and themixture was stirred. The mixture was quenched with water and extractedwith dichloromethane. The extracts were dried (MgSO₄) and evaporated.The residue product was purified by silica gel chromatography to givethe title product, ¹H N.M.R. δ(ppm) 2.10 (s, 3H, ArCH₃), 2.20 (s, 3H,ArCH₃) and 3.35 (s, 3H, NCH₃).

EXAMPLE 17N-Cyano-N′-[4-(4-chloro-3-trifluoromethylphenoxy)-2,5-xylyl]formamidine

(Compound 397)

The title compound was prepared according to Example 4 from the productof stage b) above, m.p. 111-4° C.

Preparation of Starting Materials

a) 2-Nitro-5-(4-chloro-3-trifluoromethylphenoxy)-p-xylene

The title compound was prepared according to Example 2 stage a).

b) 4-(4-Chloro-3-trifluoromethylphenoxy)-2,5-xylidine

The title compound was prepared according to Example 1 stage b) from theproduct of stage a) above.

The following compounds of formula Ia (see Table 1), i.e. compounds ofgeneral formula I where —A—R⁶ is para to the amidine moiety, may beprepared by methods analogous to those of Examples 1 to 17. Where themoiety depicted on the right side of linkage A is attached to R⁶;

TABLE 1 Cmp R¹ R² R³ R⁴ (R⁵)_(m) A R⁶ m.p./° C. 1 H Me Me Me 5-Me O3-CF₃—phenyl 49-50 2 Me Me Me Me 5-Me O 3-CF₃—phenyl oil 3 H Me Me Me5-Me —SCH₂— 3-CF₃—phenyl oil 4 H Me Me Me 5-Me S 3-CF₃—phenyl oil 5 MeMe Me Me 5-Me —SCH₂— 3-CF₃—phenyl oil 6 Me Me Me Me 5-Me S 3-CF₃—phenyloil 7 H Me Me Me 5-Me O 3-Cl—phenyl oil 8 H Me Me Me 5-Me O3-Bu^(t)—phenyl 69-71 9 H Me Me Me 5-Me O 4-tolyl oil 10 Me Me Me Me5-Me —OCH₂— 3-CF₃—phenyl oil 11 H Me Me Me 5-Me —OCH₂— 3-CF₃—phenyl50-4  12 H Me Me Me 5-Me, O 3-CF₃—phenyl oil 6-Br 13 H Me Me Me — O3-CF₃—phenyl oil 14 H Me Me CF₃ — O 3-CF₃—phenyl oil 15 H Me Me Br 5-OMeO 3-CF₃—phenyl 68-70 16 H Me Me Me 5-Me —OCH(Me)— 3-CF₃—phenyl 97-9  17H Me Me Me 5-Me —OCH₂— 3-PhO—phenyl oil 18 H Me Me Br 3-Me, O3-CF₃—phenyl oil 6-Br 19 H Me Me Br 5-Me O 3-CF₃—phenyl oil 20 H Me MeMe 6-Me O 3-CF₃—phenyl oil 21 H Me Me Me 5-Pr^(i) O 3-CF₃—phenyl oil 22H Me Me Me 5-Me O 2-biphenylyl oil 23 H Me Me Me 5-Me O 3-F—phenyl oil24 H Me Me Me 5-Me O 4-CF₃—phenyl oil 25 H Me Me Me 5-Me O 2-CF₃—phenyloil 26 H Me Me Me 5-Me O 3,4-diMeO—phenyl oil 27 H Me Me Me 5-Me O2-MeO—phenyl oil 28 H Me Me Me 5-Me O 3-PhO—phenyl oil 29 H Me Me Me5-Me O 3-CN—phenyl oil 30 H Me Me Me 5-Me O benzoxazol-2-yl 107-9  31 HMe Me Me 5-Me O 2,6-xylyl oil 32 H Me Me Me 5-Me O 3,4-diCl—phenyl oil33 H Me Me Me 5-Me O 3-EtOC(═O)—phenyl oil 34 H Me Me Me 5-Me O 4-tolyloil 35 H —(CH₂)₂O(CH₂)₂— Me 5-Me O 3-CF₃—phenyl oil 36 H H Me Me 5-Me O3-CF₃—phenyl 122-3  37 H Et Et Me 5-Me O 3-CF₃—phenyl oil 38 H Pr Pr Me5-Me O 3-CF₃—phenyl oil 39 H Bu Bu Me 5-Me O 3-CF₃—phenyl oil 40 HPr^(i) Pr^(i) Me 5-Me O 3-CF₃—phenyl oil 41 H —(CH₂)₄— Me 5-Me O3-CF₃—phenyl 71-3  42 H Ph Me Me 5-Me O 3-CF₃—phenyl oil 43 H —(CH₂)₅—Me 5-Me O 3-CF₃—phenyl oil 44 H H CN Me 5-Me O 3-CF₃—phenyl 138-40  45 HEt Me Me 5-Me O 3-CF₃—phenyl oil 46 H Pr H Me 5-Me O 3-CF₃—phenyl 44-6 47 H benzyl H Me 5-Me O 3-CF₃—phenyl 121-3  48 H Me Me Me 5-Me O3-Ph-1,2,4-thiadiazol- 100-5  5-yl 49 H Me Me Me 5-Me —OCH(Me)—3-CF₃—phenyl 97-9  50 H Me Me Me 5-Me O 4-CF₃—phenyl oil 51 H Me Me Me5-Me O 2-CF₃—phenyl oil 52 H Me Me Me 5-Me O 3-Cl-5-CF₃-2-pyridyl oil 53H Me Me Me 5-Me direct bond 3-CF₃—phenyl oil 54 H Me Me Me 5-Me O4,6-diMe—pyrimidin-2-yl 95-9  55 H Me Me Me 5-Me O 3,5-diCl—phenyl 67-9 56 H Me Me Me 5-Me O 3-MeO—phenyl oil 57 H cyHex H Me 5-Me O3-CF₃—phenyl 93-4  58 H Pr^(i) H Me 5-Me O 3-CF₃—phenyl 62.5-4.5  59 HEt H Me 5-Me O 3-CF₃—phenyl 100-2  60 H Me Me Me 5-Me —NH—C(═O)—3,5-diMe-4-oxazolyl 215-8  61 H Me Me Me 5-Me O 4-Bu^(t)—phenyl 95-6  62H HO H Me 5-Me O 3-CF₃—phenyl 130-1  63 H MeO H Me 5-Me O 3-CF₃—phenyl59-61 64 H EtO H Me 5-Me O 3-CF₃—phenyl 68-9  65 H Me Me Me 5-Me Ophenyl oil 66 H Me Me Me 5-Me O 3-Cl-1,2,4-thiadiazol- 120-2  5-yl 67 HMe Me Pr^(i) 5-Me O 3-CF₃—phenyl oil 68 H Me Me Me 5-Cl O3-Ph-1,2,4-thiadiazol-  99-101 5-yl 69 H Me Me Me 5-Me SO₂ 3-CF₃—phenyl122-3  70 H Me Me Me 5-Me —N(Me)—Cl(═O)— 3,5-diMe—isoxazol-4-yl oil 71 HMe Me Me 3-Me O 3-CF₃—phenyl oil 72 H Me Me Me 5-Me O3-Br-1,2,4-thiadiazol- 129-31  5-yl 73 H Me Me Me 5-Me —NHC(═O)— phenyl180-1  74 H Me Me Me 5-Me —N(Me)C(═O)— phenyl oil 75 H Me Me Me 5-Medirect bond piperidinyl 93-4  76 H Me Me Me 5-Me O

124-6  77 H Me Me Me 5-Me O 7-Cl-4-quinazolinyl 160-2  78 H Me Me Me5-Me O

170-2  79 H Me Me Me 5-Me direct bond 2,5-diMe-1-pyrrolyl 90-1  80 H MeMe Me 5-Me direct bond phthalimido 170-3  81 H Me Me Me 5-Me O5-CF₃-1,3,4- oil thiadiazol-2-yl 82 H Me Me Me 5-Me O 5-Bu^(t)-1,3,4-104-6  thiadiazol-2-yl 83 H Me Me Me 5-Me O 5-Ph-1,3,4-thiadiazol- oil2-yl 84 H Me Me Me 5-Me O 6-Cl—benzthiazol-2-yl 109-11  85 H Me Me Me5-Me O 5-NO₂-2-thiazolyl oil 85 H Me Me Me 5-Me O 5-Ph-2-thiazolyl111-14  87 H Me Me Me 5-Me direct bond morpholino 93-4  88 H Me Me Me5-Me O 8-F-4-quinazolinyl  98-100 89 H Me Me Me 5-Me O 3,6-diNO₂-4-178-81  coumarinyl 90 H Me Me Me 5-Me O 2-F—phenyl oil 91 H Me Me Me5-Me O 4,6-diMeO-1,3,5- 82-4  triazin-2-yl 92 H Me Me Me 5-Me directbond 3-Et₂NC(═O)-1- oil piperidinyl 93 H Me Me Me 5-Me S

oil 94 H Me Me Me 5-Me S 4-(4-Cl—phenyl)-2- oil oxazolyl 95 H Me Me Me5-Me O 4-(4-Cl—phenyl)-2- oil oxazolyl 96 H Me Me Me 5-Me O2-CF₃-4-quinazolinyl 119-21  97 H Me Me Me 5-Me direct bond4,5-diCl—phthalimido 196-8  98 H Me Me Me 5-Me —NHC(═O)— 4-F—phenyl166-8  99 H CN H Me 5-Me O 3-Bu^(t)—phenyl oil 100 H Et Me Me 5-Me O3-Bu^(t)—phenyl oil 101 H Me Me Me 5-Me O 4-CF₃—pyrimidin-2-yl 123-5 102 H Me Me Me 5-Me direct bond 2,6-diMe—morpholin- 102-3  4-yl 103 H MeMe Me 5-Me O 2-CF₃-4-quinolinyl 126-8  104 H Me Me Me 5-Me O 2-tolyl oil105 H Me Me Me 5-Me O 2-Pr^(i)—phenyl oil 106 H Et H Me 5-Me O3-Bu^(t)—phenyl 74-6  107 Et Me Me H 5-Me O 3-Bu^(t)—phenyl 89-91 108 MeMe Me H 5-Me O 3-Bu^(t)—phenyl oil 109 H Me Me H 5-Me O 3-Bu^(t)—phenyloil 110 Et Me Me Me 5-Me O 3-Bu^(t)—phenyl 113-6  111 H Me Me Me 5-Medirect bond 4-Me-1-piperazinyl 67-8  112 H Me Me Me 5-Me O4-(2-thiazolyl)-2- 110-12  thiazolyl 113 H Me Me Me 5-Me O4-Bu^(t)-2-thiazolyl oil 114 H Me Me Me 5-Me O 3-(4-Cl—phenyl)-1,2,4-106-8  oxadiazol-5-yl 115 H Me Me Me 5-Me direct bond2-Me-5-(3-CF—phenyl)- oil 1-pyrrolyl 116 H Me Me Me 5-Me O 3-MeO-1,2,4- 99-101 thiadiazol-5-yl 117 H Me Me Me 5-Me O 3-Me-1,2,4-thiadiazol-92-4  5-yl 118 H Me Me Me 5-Me O 6-Ph-3-pyridazinyl 86-9  119 H Me Me Me5-Me O 3-MeS-1,2,4- oil thiadiazol-6-yl 120 H Me Me Me 5-Me O4-(3-CF₃—phenyl)-2- 93-5  thiazolyl 121 H Me Me Me 5-Me S4-Me-1,2,4-triazol-3-yl oil 122 H Me Me Me 5-Me O 3-CN-2-pyrazinyl128-30  123 H Me Me Me 5-Me O 3-Bu^(t)-1,2,4- oil thiadiazol-5-yl 124 HMe Me Me 5-Me O 2-secButyl—phenyl oil 125 H Me Me Me 5-Me O 2-biphenylyloil 126 H Me Me Me 5-Me O 5-isopropenyl-1,3,4- oil thiadiazol-2-yl 127 HMe Me Me 5-Me O 5-Ph-1,3,4-oxadiazol- 120-2  2-yl 128 H Me Me Me 5-Medirect bond 1,2,3,4-tetrahydro-2- oil isoquinolinyl 129 H Me Me Me 5-MeO 3-NEt₂—phenyl oil 130 H Me Me Me 5-Me O 4-secButyl—phenyl oil 131 H MeMe Me 5-Me O 5-Cl-6-Et—pyrimidin-4-yl 100-1  132 H Me Me Me 5-Me O2-CF₃—pyrimidin-4-yl 62-3  133 H Me Me Me 5-Me O 1-Me-5-Cl-6-oxo- 142-5 pyridazin-4-yl 134 H Me Me Me 5-Me O 3-Ph-5-isoxazolyl oil 135 H Me MeMe 5-Me O 3-Br—phenyl oil 136 H Me Me Me 5-Me O 3-(dimethyl-amino- oilmethylene- amino)phenyl 137 H Me Me Me 5-Me O 4-Cl-1,2,5-thiadiazol- oil3-yl 138 H Me Me Me 5-Me O 3-CF₃-1,2,4- oil thiadiazol-5-yl 139 H Me MeMe 5-Me O 2-Cl—phenyl oil 140 H Me Me Me 5-Me O 2-MeS-5-EtOC(═O)- oilpyrimidin-4-yl 141 H Me Me Me 5-Me O 1-naphthyl oil 142 H Me Me Me 5-MeO 2-naphthyl oil 143 Me Me Me Me 5-Me O 1-naphthyl oil 144 Me Me Me Me5-Me O 2-naphthyl 110-12  145 H Me Me Me 5-Me O 1-Ph—tetrazol-5-yl123-6  146 H Me Me Me 5-Me O 1,1-dioxo- 177-8  benzothiazol-3-yl 147 HMe Me Me 5-Me direct bond 2-benzo[b]-furanyl 90-1  148 H Me Me Me 5-Me O6-Ph—pyrimidin-4-yl oil 149 H Me Me Me 5-Me O 4-Pr^(i)—phenyl oil 150 HMe Me Me 5-Me O 3-acetylphenyl oil 151 H Me Me Me 5-Me O 4-(1,1,3,3- oiltetramethyl- butyl)phenyl 152 H Me Me Me 5-Me O 3-Pr^(i)—phenyl oil 153H Me Me Me 5-Me —OC(═O)— 3,4-diCl—phenyl oil 154 H Me Me Me 5-Me—OC(═O)— 4-hexylphenyl oil 155 H Me Me Me 5-Me —OC(═O)— 2,6-xylyl oil156 H Me Me Me 5-Me —OC(═O)CH₂— 4-Cl—phenyl oil 157 H Me Me Me 5-Me—OC(═O)CH₂— phenyl oil 158 H Me Me Me 5-Me —OC(═O)CH₂— 3-MeO—phenyl oil159 H Me Me Me 5-Me —OC(═O)— 2,6-diCl—phenyl oil 160 H Me Me Me 5-Me—OC(═O)— 3-Cl-2-benzo[b]- oil thiophenyl 161 H Me Me Me 5-Me —OC(═O)—cyclohexyl oil 162 H Me Me Me 5-Me —OC(═O)— 2,4-diCl—phenyl oil 163 H MeMe Me 5-Me —OC(═O)— 2-CF₃—phenyl oil 164 H Me Me Me 5-Me —OC(═O)—2,3-diCl—phenyl oil 165 H Me Me Me 5-Me —OC(═O)— 3,5-diMe—isoxazol-4-yloil 166 H Me Me Me 5-Me —OC(═O)— 4-Me-1,2,3-thiadiazol- oil 5-yl 167 HMe Me Me 5-Me —OC(═O)— 2-F-3-CF₃—phenyl oil 168 H Me Me Me 5-Me —OC(═O)—3-Cl-2-MeO-5-pyridyl oil 169 H Me Me Me 5-Me —OC(═O)— 2-Cl-3-pyridyl oil170 H Me Me Me 5-Me O 4-(tert-pentyl)phenyl oil 171 H Me Me Me 5-Me O3-Et—phenyl oil 172 Me Me Me Me 5-Me O 4-(tert-pentyl)phenyl oil 173 HMe Me Me 5-Me O 4-Cl-3-Me—phenyl oil 174 H Me Me Me 5-Me O 3,4-xylyl oil175 H Me Me Me 5-Me O

94-6  176 H Me Me Me 5-Me direct bond 2-thienyl oil 177 H Me Me Me 5-Medirect bond 5-Cl-2-thienyl oil 178 H Me Me Me 5-Me direct bond 3-Cl-2-114-5  benzo[b]furanyl 179 H Me Me Me H direct bond5-(4-Cl—phenyl)-1,2,4- 136-7  oxadiezol-3-yl 180 H Me Me Me 5-Me O4-nonylphenyl oil 181 H Me Me Me 5-Me O 4-Et—phenyl oil 182 H Me Me Me5-Me O 4-biphenylyl oil 183 H Me Me Me 5-Me O 4-Cl—phenyl oil 184 H MeMe Me 5-Me O 4-MeS—phenyl oil 185 H Me Me Me 5-Me O 4-Br—phenyl oil 186H Me Me Me 5-Me —OCH₂— 2-(4-Cl—phenyl)-4- 86-9  thiazolyl 187 H Me Me Me5-Me direct bond 2-benzo[b]thiophenyl 67-8  188 H Me Me Me 5-Me O2-(5,6,7,8- 84-6  tetrahydro)naphthyl 189 H Me Me Me 5-Me O 4-(α,α- oildiMe—benzyl)phenyl 190 H Me Me Me 5-Me O 3-CF₃O—phenyl oil 191 Me Me MeMe 5-Me direct bond 3-Et₂NC(═O)-1- oil piperidinyl 192 H Me Me Me 5-Me Sphenyl 72-3  193 H Me Me Me 5-Me O 4-MeO—phenyl 57-8  194 H Me Me Me5-Me O 5-CF₃-2-benzthiazolyl 106-7  195 H Me Me Me 5-Me O4-Cl-2-benzthiazolyl 109-11  196 H Me Me Me 5-Me O 5-Cl-2-benzthiazolyloil 197 H Me Me Me 5-Me O 2-benzthiazolyl oil 198 H Me Me Me 5-Me O2-Pr^(i)-5-Me—phenyl oil 199 Me Me Me Me 5-Me O 2-Pr^(i)-5-Me—phenyl oil200 H Me Me Me 5-Me O 4-Cl-3-Et—phenyl oil 201 Me Me Me Me 5-Me O4-Cl-3-Et—phenyl oil 202 H Me Me Me 5-Me O 3-Me-4-MeS—phenyl oil 203 HMe Me Me 5-Me O 4-benzoylphenyl oil 204 H Me Me Me 5-Me O4-propionylphenyl oil 205 H Me Me Me 5-Me O 4-(3-Me-1,2,4- 109.5-11  thiadiazol-5-yl)phenyl 206 Me Me Me Me 5-Me O 3-Ph-1,2,4-thiadiazol-113-4  5-yl 207 H Me Me Me H O 3-Ph-1,2,4-thiadiazol- oil 5-yl 208 H MeMe Me 5-Pr^(i) O 3-Ph-1,2,4-thiadiazol- oil 5-yl 209 Me Me Me Me H O3-Ph-1,2,4-thiadiazol- oil 5-yl 210 H Me Me Me H direct bond5-Bu^(t)-1,2,4- oil oxadiazol-3-yl 211 H Me Me Me H direct bond5-Bu^(t)1,3,4- 79-80 oxadiazol-2-yl 212 H Me Me Me 5-Me O 4-acetylphenyl80-1  213 H Me Me Me 5-Me O 3-(3- oil CF₃—phenoxy)—phenyl 214 H Me Me Me5-Me —CH(CN)— 3-CF₃—phenyl oil 215 H Me Me Me 5-Me O 4-(4-Cl—phenyl)-2-oil thiazolyl 216 H Me Me Me 5-Me O 4-(4-tolyl)-2-thiazolyl oil 217 H MeMe Me 5-Me O 4-(4-MeO—phenyl)-2- oil thiazolyl 218 H Me Me Me 5-Me O6-Cl—pyrimidin-4-yl 205-7  219 H Me Me Me 5-Me O 4-oxo-2-Ph-4H-1- oilbenzopyran-6-yl 220 H Me Me Me 5-Me O 2-(benzyloxy)phenyl oil 221 H MeMe Me 5-Me O 3,4- oil methylenedioxy—phenyl 222 H Me Me Me 5-Me O3,5-xylyl oil 223 H Me Me Me 5-Me O 3,5-diMeO—phenyl oil 224 H Me Me Me5-Me O 6-PhO—pyrimidin-4-yl oil 225 H Et Me Me 5-Me O3-Ph-1,2,4-thiadiazol- oil 5-yl 226 H Me Me Me 5-Me direct bond 3-Cl-2-84-6  benzo[b]thiophenyl 227 H CN H Me 5-Me O 3-Ph-1,2,4-thiadiazol- oil5-yl 228 H Me Me Me H direct bond 5-(4-Cl—phenyl)-1,3,4- 168-9 oxadiazol-2-yl 229 Me Me Me Me H direct bond 5-(4-Cl—phenyl)-1,3,4-133-5  oxadiazol-2-yl 230 Me Me Me Me 5-Me O 3-Pr^(i)—phenyl oil 231 HMe Me Me 5-Me —CH(CO₂Me)— 3-CF₃—phenyl oil 232 H Et H Me 5-Me O3-Ph-1,2,4-thiadiazol- oil 5-yl 233 Me Me Me Me H direct bond5-Bu^(t)-1,3,4- oil oxadiazol-2-yl 234 H Me Me Me 5-Me O3-(4-tolyl)-1,2,4- 121-4  thiadiazol-5-yl 235 H Me Me Me 5-Me O4-propargyloxyphenyl oil 236 H Me Me Me 5-Me O 6-Br-2-pyridyl oil 237 MeMe Me H 5-Me O 3-Ph-1,2,4-thiadiazol- oil 5-yl 238 Me Me Me Me 5-Me O3-Br—phenyl oil 239 Me Me Me Me 5-Me O 4-Et—phenyl oil 240 Me Me Me Me5-Me O 4-biphenylyl oil 241 Me Me Me Me 5-Me O 4-Cl—phenyl oil 242 Me MeMe Me 5-Me O 4-MeS—phenyl oil 243 Me Me Me Me 5-Me O 4-Br—phenyl oil 244Me Me Me Me 5-Me O 4-benzoylphenyl oil 245 Me Me Me Me 5-Me O4-propionylphenyl oil 246 H —(CH₂)₅— Me 5-Me O 3-Ph-1,2,4-thiadiazol-oil 5-yl 247 H Me Me Me H O 5-CF₃-1,3,4- oil thiadiazol-2-yl 248 H Me MeMe 5-Me O 6- oil (trimethylsilylethynyl)- 2-pyridyl 249 H Me Me Me 5-MeO 6-ethynyl-2-pyridyl oil 250 H Me Me Me 5-Me O 2,4-diCl—phenyl 96-7 251 H Me Me Me 5-Me O 5-Pr^(i)-2-Me—phenyl oil 252 H Me Me Me 5-Me O3-(4-Cl—phenyl)-1,2,4- 118-22  thiadiazol-5-yl 253 H Me Me Me 5-Me O3-(3-NO₂—phenyl)- 125-8  1,2,4-thiadiazol-5-yl 254 Et Me Me Me 5-Me O3-Ph-1,2,4-thiadiazol- oil 5-yl 255 Et Me Me H 5-Me O3-Ph-1,2,4-thiadiazol- oil 5-yl 256 H Me Me Me 5-Me O4-Pr^(i)-3-Me—phenyl oil 257 H Me Me H H O 3-Bu^(t)—phenyl oil 258 H MeMe Me 5-Me O 9-oxo-fluoren-2-yl oil 259 H Me Me Me 5-Me O3-(3,5-diCF₃—phenyl)- 112-5  1,2,4-thiadiazol-5-yl 260 H Me Me Cl H O3-Bu^(t)—phenyl oil 261 H Me Me Me 5-Me O 4-benzyloxyphenyl oil 262 H MeMe Me 5-Me O 6-(4-Cl—phenyl)-2- oil pyridyl 263 H Me Me Me 5-Me O4-HO—phenyl oil 264 H Me Me Me 5-Me O 3-CF₃—benzyl 75-7  265 H Me Me Me5-Me O 6-(3-CF₃—phenylthio)- oil pyrimdin-4-yl 266 H Me Me Me 5-Me O3-benzyloxyphenyl oil 267 H Me Me Me 5-Me —OCH₂— cyclohexyl oil 268 H MeMe Me 5-Me —OCH₂CH₂O— 4-Cl—phenyl oil 269 H Me Me Me 5-Me —OCH₂CH₂O—4-Bu^(t)—phenyl oil 270 H Me Me Me 5-Me —O(CH₂)₄O— phenyl oil 271 H MeMe Me 5-Me —O(CH₂)₄— phthalimido oil 272 H Me Me Me 5-Me —O(CH₂)₅—phenyl oil 273 H Me Me Me 5-Me —O(CH₂)₃O— 4-Bu^(t)—phenyl oil 274 H MeMe Me 5-Me —O(CH₂)₄O— 4-Bu^(t)—phenyl oil oil 275 H Me Me Me 5-Me—O(CH₂)₄O— 2-Bu^(t)—phenyl oil 276 H Me Me Me 5-Me —OCH₂—2-tetrahydropyranyl oil 277 H Me Me Me 5-Me —O(CH₂)₃O— phenyl oil 278 HMe Me Me 5-Me —O(CH₂)₉O— 2-tetrahydropyranyl oil 279 H Me Me Me 5-Me—OCH₂— 2-(1-methoxy- oil carbonyl-2- methoxyvinyl)phenyl 280 H Me Me Me5-Me —OCH₂CH₂— 2-phenylethyl oil 281 H Pr Me Me 5-Me O 3-Bu^(t)—phenyloil 282 H Bu Me Me 5-Me O 3-Bu^(t)—phenyl oil 283 H Pr^(i) Me Me 5-Me O3-Bu^(t)—phenyl oil 284 H allyl Me Me 5-Me O 3-Bu^(t)—phenyl oil 285 HBu Et Me 5-Me O 3-Bu^(t)—phenyl oil 286 H Et Et Me 5-Me O3-Bu^(t)—phenyl oil 287 H Me Me Me 5-Me O 6-Bu^(t)S—pyrimidin-4-yl oil288 H Me Me Me 5-Me O 3,3-diMe-2-EtO-2,3- oil dihydrobenzfuran-5-yl 289H Me Me Me 5-Me O 6-cyHexS—pyrimidin-4- oil yl 290 H Me Me Me 5-Me—OCH₂— 4- oil cyHexylmethyloxy—phenyl 291 H Me Me Me 5-Me O3-Pr^(i)O—phenyl oil 292 H Me Me Me H O 2-(2- oil phenoxy—ethoxy)phenyl293 H CN H H 5-Me O 3-Ph-1,2,4-thiadiazol- 152-4  5-yl 294 H Me Me Cl HO 3-CF₃—phenyl oil 295 H Me Me Me 5-Me O 6-(2-phenylethyl- oilthio)pyrimidin-4-yl 296 H Me Me Me 5-Me O 4-(3- oil CF₃—benzyloxy)phenyl297 H Me Me CF₃ H O 3-Bu^(t)—phenyl oil 298 H Me Me Me 5-Me O4-(2-Cl—phenyl)thiazol- oil 2-yl 299 H Me Me Me 5-Me O4-(3-Cl—phenyl)thiazol- 122-5  2-yl 300 H Me Me Me 5-Me O4-(4-CF₃—phenyl)hiazol- 123-5  2-yl 301 H Me Me Me 5-Me O 3-(3- oilCF₃—benzyloxy)phenyl 302 H Me Me Me 5-Me O 2-(4- oil Me—butoxy)phenyl303 H Me Me Me 5-Me O 4-Pr^(i)O—phenyl oil 304 H Me Me Me 5-Me-6- O3-Bu^(t)—phenyl oil NO₂ 305 H Me Me Me 5-Me O 2-(3- oilCF₃—benzyloxy)phenyl 306 H Me Me Me H O 2-(3- oil CF₃—benzyloxy)phenyl307 H CN H Me 5-Me O 3-Cl—phenyl 134-5  308 H CN H Me 5-Me O4-Pr^(i)—phenyl 159-60  309 H CN H Me 5-Me O 3-MeO—phenyl 104-8  310 HEt Me Me 5-Me O 3-Cl—phenyl oil 311 H Et Me Me 5-Me O 4-Pr^(i)—phenyloil 312 H Et Me Me 5-Me O 3-MeO—phenyl oil 313 H Et Me Me 5-Me O4-(tert-pentyl)phenyl oil 314 H Me Me Me 5-Me O 3-(1- oilMe—undecyloxy)phenyl 315 H Me Me Me 5-Me O 2-Pr^(i)O—phenyl oil oil 316H Me Me Me 5-Me O 3,5-diPr^(i)—phenyl oil 317 H Me Me Me 5-Me O3-MeO-5-Me—phenyl oil 318 H Me Me Me 5-Me O 3,5-diCF₃—phenyl oil 319 HMe Me Me 5-Me O 2-(1- oil Me—undecycloxy)phenyl 320 H Me Me Me H O2-(isopentoxy)phenyl oil 321 H Me Me Me H O 2-Pr^(i)O—phenyl oil 322 HMe Me Me 5-Me O 6-Cl—benzoxazol-2-yl 118-20  323 H CN H Me 5-Me O3-PhO—phenyl oil 324 H CN H Me 5-Me O 4-Bu^(t)—phenyl oil 325 H Et Me Me5-Me O 3-PhO—phenyl oil 326 H Et Me Me 5-Me O 4-Bu^(t)—phenyl oil 327 HMe Me Me 5-Me O 5-Cl—benzoxazol-2-yl 190 328 H Me Me Me 5-Me O5-NO₂—benzoxazol-2- oil yl 329 H allyl Me Me 5-Me O 3-CF₃—phenyl oil 330H Pr Me Me 5-Me O 3-CF₃—phenyl oil 331 H Bu Me Me 5-Me O 3-CF₃—phenyloil 332 H Me Me Me 5-Me O 3-HO—phenyl 155-7  333 H CN H Me 5-Me O3,5-diCl—phenyl 199-201 334 H Me Me Me 5-Me O 3-(3-Ph-1,2,4- oilthiadazol-5- yloxy)phenyl 335 H Et Me Me 5-Me O 3,5-diCl—phenyl oil 336H Me Me Me 5-Me O 5-Br—benzthiazol-2-yl oil 337 H Me Me Me 5-Me O 5-(4-131-3  CF₃—phenyl)benzthiazol- 2-yl 338 H Me Me Me 5-Me O5-Ph—benzthiazol-2-yl 107-9  339 H Me Me Me 5-Me O 5-(4-CF₃O—phenyl)-138-40  benzthiazol-2-yl 340 H Me Me Me 5-Me O 3-(isopentoxy)phenyl oil341 H Me Me Me 5-Me O 3- oil (cyclohexylmethoxy)phenyl 342 H Me Me Me5-Me O 3-(4- oil biphenylylmethoxy)- phenyl 343 H Me Me Me 5-Me O 3- oil(propargyloxy)phenyl 344 H Me Me Me 5-Me O 3-(allyloxy)phenyl oil 345 HMe Me Me 5-Me O 3-(PhO—ethoxy)phenyl oil 346 H Me Me Me 5-Me O3-(2-thienyl)phenyl oil 347 H Me Me Me 5-Me, O 3-Bu^(t)—phenyl oil 6-Br348 H Me Me Me 5-Me O 3-(cyclopropyl- oil methoxy)phenyl 349 H Me Me Me5-Me O 3-(phenacyloxy)- oil phenyl 350 H Me Me Me 5-Me O3-(methoxycarbonyl- oil methyl)phenyl 351 H Me Me Me 5-Me O 4-(3,4-121-3  diCl—phenyl)thiazol-2-yl 352 H Me Me Me 5-Me O3-(benzyloxycarbonyl- oil methoxy)phenyl 353 H Me Me Me 5-Me O3-(3-Cl-4- oil F—phenyl)phenyl 354 H Me Me Me 5-Me O3-(tetrahydrofuran-2- oil ylmethoxy)phenyl 355 H Me Me Me 5-Me O3-(tetrahydropyran-2- oil ylmethoxy)phenyl 356 H Me Me Me 5-F O3-Ph-1,2,4-thiadiazol- 67-9  5-yl 357 H Me Me Me 5-Me O 4-(4- oilCl—benzoyl)phenyl 358 H Me Me Me 5-Me O 3-[1-(ethoxycarbonyl)- oilethoxy]phenyl 359 H Me Me Me 5-Me O 3-(2,2,2- oil trifluoroethoxy)phenyl360 H Me Me Me 5-Me O 3-(4- oil CN—butoxy)phenyl 361 H Me Me Me 5-Me O4-Cl-3-CF₃—phenyl oil 362 H Me Me Me 5-Me O 5-CF₃—benzthiazol- oil 2-yl363 H Me Me Me 5-F O 3-CF₃—phenyl oil 364 H Et Me Me 5-Me O4-Cl-3-CF₃—phenyl oil 365 H Me Me Me 5-Me O 4-F-3-CF₃—phenyl oil 366 HMe Me Me 5-Me O 3-iodo-phenyl oil 367 H Me Me Me 5-Me O 3-acetoxyphenyloil 368 H Me Me Me 5-Me O 5-CF₃—benzthiazol- oil 2-yl 369 H Me Me Me5-Me O 3-(4,6-diMe—pyrimidin- oil 2-yloxy)phenyl 370 H Me Me Me 5-Me O3-Bu^(i)—phenyl oil 371 H Me Me Me 5-Me O 3-(1-benzoyl-1- oilmethylethoxy)phenyl 372 H Me Me Me 5-Me O 3-(1-ethoxycarbonyl- oil2-methylprop-1- yloxy)phenyl 373 H CN Me Me 5-Me O 4-Cl-3-CF₃—phenyl oil374 H Et CN Me 5-Me O 4-Cl-3-CF₃—phenyl oil 375 H Ac CN Me 5-Me O4-Cl-3-CF₃—phenyl oil 376 H Me Me Me 5-Me O 3-(1-acetylethoxy)- oilphenyl 377 H Me Me Me 5-Me O 3-(1-ethylpropoxy)- oil phenyl 378 H Me MeMe 5-Me O 3-cyclopentylphenyl oil 379 H Me Me Me 5-Me O 3-(3,5-diCl-2-oil pyridyloxy)phenyl 380 H Me Me Me 5-Me O 3-[ethoxycarbonyl-(N- oilmethoxyimino)- methoxy]phenyl 381 H Me Me Me 5-Me O 4-(2- oilCF₃—benzoyl)phenyl 382 H Me Me Me 5-Me O 3-hexylphenyl oil 383 H Me MeMe 5-Me O 5-Ph—thiazol-2-yl oil 384 H Me Me Me 5-Me O 3-(2,2-dimethoxy-oil ethoxy)phenyl 385 H Me Me Me 5-Me O 3-(2,2- oil diethoxyethoxy)-phenyl 386 H Me Me Me 5-Me O 3-[2-(3- oil Bu^(t)—phenoxy)- ethoxy]phenyl387 H Me Me Me 5-Me O 3-[2-(4-F—phenoxy)- 102-4  ethoxy]phenyl 388 H MeMe Me 5-Me O 3-CF₃SO₂O—phenyl oil 389 H Me Me Me 5-Me O 4-Br-3-Cl—phenyl86-8  390 H Me Me Me 5-Me O 3-(2-Me-2- oil phenypropyl)-phenyl 391 H MeMe Me 5-Me O 3-(1-HO-1-Me—ethyl)- oil phenyl 392 H Me Me Me 5-Me O3-(1-MeO-1- oil Me—ethyl)-phenyl 393 H Et Me Me 5-Me O 4-F-3-CF₃—phenyloil 394 H Me Me Me 5-Me O 4-Me-3-CF₃—phenyl oil 395 H Et Me Me 5-Me O4-Me-3-CF₃—phenyl oil 396 H —(CH₂)₅— Me 5-Me O 3-Bu^(t)—phenyl oil 397 HH CN Me Me O 3-CF₃-4-Cl—phenyl- 111-4  398 H Me Me Me Me C═O3-CF₃—phenyl oil

Those compounds in Table 1 which do not have discrete melting pointshave the characteristic ¹H N.M.R. shown in Table 2 below.

TABLE 2 Cmp Data 2 1.78 (s, 3H, N═CCH₃), 2.00 (s, 3H, ArCH₃), 2.18 (s,3H, ArCH₃), 3.05 (s, 6H, N(CH₃)₂) 3 2.15 (s, 3H, ArCH₃), 2.20 (s, 3H,ArCH₃), 3.00 (s, 6H, N(CH₃)₂), 3.95 (s, 2H, SCH₂) 4 2.00 (s, 3H, ArCH₃),2.20 (s, 3H, ArCH₃), 3.00 (s, 6H, N(CH₃)₂) 5 1.70 (s, 3H, N═CCH₃), 1.90(s, 3H, ArCH₃), 2.10 (s, 3H, ArCH₃), 3.00 (s, 6H, N(CH₃)₂), 3.90 (s, 2H,SCH₂) 6 1.80 (s, 3H, N═CCH₃), 2.00 (s 3H, ArCH₃), 2.20 (s, 6H, N(CH₃)₂),3.00 (s, 6H, N(CH₃)₂) 7 2.10 (s, 3H, ArCH₃), 2.20 (s, 3H, ArCH₃), 3.00(s, 6H, N(CH₃)₂) 9 2.10 (s, 3H, ArCH₃), 2.20 (s, 3H, ArCH₃), 2.30 (s,3H, ArCH₃), 3.00 (s, 6H, N(CH₃)₂) 10 1.75 (s, 3H, N═CCH₃), 2.00 (s, 3H,ArCH₃), 2.20 (s, 3H, ArCH₃), 3.00 (s, 6H, N(CH₃)₂), 5.10 (s, 2H, ArCH₂12 2.17 (s, 3H, ArCH₃), 2.22 (s, 3H, ArCH₃), 3.05 (s, 6H, N(CH₃)₂) 132.25 (s, 3H, ArCH₃), 3.00 (s, 6H, N(CH₃)₂) 14 3.00 (s, 6H, N(CH₃)₂) 172.18 (s, 3H, ArCH₃), 2.22 (s, 3H, ArCH₃), 2.99 (s, 6H, N(CH₃)₂), 5.00(s, 2H, ArCH₂) 18 2.20 (s, 3H, ArCH₃), 3.00 (bs, 6H, N(CH₃)₂) 19 2.10(s, 3H, ArCH₃), 3.00 (s, 6H, N(CH₃)₂) 20 2.15 (s, 6H, ArCH₃), 3.00 (s,6H, N(CH₃)₂) 21 1.15 (d, 6H, CH(CH₃)₂), 2.20 (s, 3H, ArCH₃), 3.00 (m,7H, CH and N(CH₃)₂) 22 2.15 (s, 3H, ArCH₃), 2.22 (s, 3H, ArCH₃), 3.04(s, 6H, N(CH₃)₂) 23 2.10 (s, 3H, ArCH₃), 2.22 (s, 3H, ArCH₃), 3.02 (s,6H, N(CH₃)₂) 24 2.10 (s, 3H, ArCH₃), 2.20 (s, 3H, ArCH₃), 3.00 (s, 6H,N(CH₃)₂) 25 2.10 (s, 3H, ArCH₃), 2.20 (s, 3H, ArCH₃), 3.00 (s, 6H,N(CH₃)₂) 26 2.14 (s, 3H, ArCH₃), 2.19 (s, 3H, ArCH₃), 3.00 (s, 6H,N(CH₃)₂, 3.82 (s, 3H, OCH₃), 3.96 (s, 3H, OCH₃) 27 2.14 (s, 3H, ArCH₃),2.18 (s, 3H, ArCH₃), 3.00 (s, 6H, N(CH₃)₂), 3.93 (s, 3H, OCH₃) 28 2.13(s, 3H, ArCH₃), 2.19 (s, 3H, ArCH₃), 3.00 (s, 6H, N(CH₃)₂) 29 2.08 (s,3H, ArCH₃), 2.22 (s, 3H, ArCH₃), 3.00 (s, 6H, N(CH₃)₂) 31 2.07 (s, 3H,ArCH₃), 2.11 (s, 6H, ArCH₃), 2.36 (s, 3H, ArCH₃), 3.00 (s, 6H, N(CH₃)₂)32 2.08 (s, 3H, ArCH₃), 2.20 (s, 3H, ArCH₃), 3.01 (s, 6H, N(CH₃)₂) 331.38 (t, 3H, CH₂CH₃), 2.09 (s, 3H, ArCH₃), 2.20 (s, 3H, ArCH₃), 3.03 (s,6H, N(CH₃)₂), 4.35 (q, 2H, CH₂) 34 (s, 3H, ArCH₃), 2.19 (s, 3H, ArCH₃),2.26 (s, 3H, ArCH₃), 3.00 (s, 6H, N(CH₃)₂) 35 2.05 (s, 3H, ArCH₃), 2.20(s, 3H, ArCH₃), 3.45-3.55 (br, 4H, CH₂), 3.75 (d, 4H, CH₂) 37 1.20 (t,6H, CH₂CH ₃), 2.10 (s, 3H, ArCH₃), 2.20 (s, 3H, ArCH₃), 3.30-3.50 (br,4H, CH ₂CH₃) 38 0.95 (t, 6H, CH₂CH ₃), 1.70 (br, 4H, CH₃CH ₂), 2.10 (s,3H, ArCH₃), 2.20 (s, 3H, ArCH₃), 3.10-3.50 (br, 4H, NCH₂) 39 1.00 (t,6H, CH₂CH ₃), 1.35 (q, 4H, CH ₂CH₃), 1.60 (q, 4H, NCH₂ CH ₂ ), 2.10 (s,3H, ArCH₃), 2.20 (s, 3H, ArCH₃), 3.15-3.45 (br, 4H, NCH₂) 40 1.3 (d,12H, CCH₃), 2.10 (s, 3H, ArCH₃), 2.20 (s, 3H, ArCH₃), 3.6-4.9 (br, 2H,CH) 42 2.10 (s, 3H, ArCH₃), 2.30 (s, 3H, ArCH₃), 3.55 (s, 3H, NCH₃) 431.55-1.75 (m, 6H, CH ₂), 2.10 (s, 3H, ArCH₃), 2.20 (s, 3H, ArCH₃), 3.40(br, 4H, NCH₂) 45 1.20 (t, 3H, CH₂CH₃), 2.10 (s, 3H, ArCH₃), 2.20 (s,3H, ArCH₃), 3.00 (s, 3H, NCH₃), 3.40 (br, 2H, NCH₂) 50 2.10 (s, 3H,ArCH₃), 2.20 (s, 3H, ArCH₃), 3.00 (s, 6H, N(CH₃)₂) 51 2.10 (s, 3H,ArCH₃), 2.20 (s, 3H, ArCH₃), 3.00 (s, 6H, N(CH₃)₂) 52 2.18 (s, 6H,ArCH₃), 2.98 (s, 6H, N(CH₃)₂) 53 2.00 (s, 3H, ArCH₃), 2.20 (s, 3H,ArCH₃), 3.00 (s, 6H, (NCH₃)₂) 56 2.09 (s, 3H, ArCH₃), 2.19 (s, 3H,ArCH₃), 3.00 (s, 6H, N(CH₃)₂) and 3.77 (s, 3H, OCH₃) 65 2.1 (s, 3H,ArCH₃), 2.2 (s, 3H, ArCH₃) and 3.0 (s, 6H, N(CH₃)₂) 67 1.15 (d, 6H,CH(CH₃)₂), 2.10 (s, 3H, ArCH₃), 3.05 (s, 6H, N(CH₃)₂) and 3.43 (m, 1H,CH(CH₃)₂) 70 2.20 (s, 6H, ArCH₃O, 1.85 (s, 3H, CH₃), 1.90 (s, 3H, CH₃),3.00 (s, 6H, N(CH₃)₂), 3.35 (s, 3H, NCH₃) 71 2.05 (s, 3H, ArCH₃), 2.28(s, 3H, ArCH₃) and 3.00 (s, 6H, N(CH₃)₂) 74 2.06 (s, 3H, ArCH₃), 2.13(s, 3H, ArCH₃), 3.00 (s, 6H, N(CH₃)₂) and 3.35 (s, 3H, CONCH₃) 81 2.10(s, 3H, ArCH₃), 2.20 (s, 3H, ArCH₃), 3.00 (s, 3H, N(CH₃)₂) 83 2.21 (s,3H, ArCH₃), 2.22 (s, 3H, ArCH₃), 3.02 (s, 6H, N(CH₃)₂) 85 2.10 (s, 3H,ArCH₃), 2.19 (s, 3H, ArCH₃), 2.97 (s, 6H, N(CH₃)₂) 90 2.16 (s, 3H,ArCH₃), 2.20 (s, 3H, ArCH₃), 3.01 (s, 6H, N(CH₃)₂) 92 1.00 (t, 6H,(NCH₂CH₃)₂), 2.10 (s, 3H, ArCH₃), 2.20 (s, 3H, ArCH₃), 3.00 (s, 6H,N(CH₃)₂), 3.35 (m, 4H, N(CH ₂CH₃)₂) 93 2.20 (s, 6H, ArCH₃), 3.00 (s, 6H,N(CH₃)₂) 94 2.20 (s, 6H, ArCH₃), 3.00 (s, 6H, N(CH₃)₂) 95 2.1 (s, 3H,ArCH₃), 2.20 (s, 3H, ArCH₃), 3.00 (s, 6H, N(CH₃)₂) 99 1.30 (s, 9H,C(CH₃)₃), 2.30 (m, 6H, ArCH₃), 100 1.20 (t, 3H, NCH₂CH₃), 1.30 (s, 9H,C(CH₃)₃), 2.10 (s, 3H, ArCH₃), 2.20 (s, 3H, ArCH₃), 3.0 (s, 3H, NCH₃),3.40 (b, 2H, NCH ₂CH₃ 104 2.12 (s, 3H, ArCH₃), 2.20 (s, 3H, ArCH₃), 2.37(s, 3H, ArCH₃), 3.02 (s, 6H, N(CH₃)₂) 105 1.30 (d, 6H, CHCH₃), 2.16 (s,3H, ArCH₃), 2.20 (s, 3H, ArCH₃), 3.01 (s, 6H, N(CH₃)₂), 3.43 (m, 1H,CH(CH₃)₂) 108 1.30 (s, 3H, C(CH₃)3), 1.95 (s, 3H, CCH₃), 2.15 (s, 3H,ArCH₃) 3.00 (s, 6H, N(CH₃)₂) 109 1.30 (s, 9H, C(CH₃)3), 2.20 (s, 3H,ArCH₃), 3.00 (s, 6H, N(CH₃)₂) 110 1.00 (t, 3H, CH₂CH₃, 1.25 (s, 9H,C(CH₃)₃), 2.00 (s, 3H, ArCH₃), 2.10 (s, 3H, ArCH₃), 2.25 (q, 2H, CH₂CH₃), 3.05 (s, 6H, N(CH₃)₂) 113 1.31 (s, 9H, C(CH₃)₃), 2.19 (s, 3H,ArCH₃), 2.22 (s, 3H, ArCH₃), 3.03 (s, 6H, N(CH₃)₂), 115 1.74 (s, 3H,pyrrCH₃), 2.00 (s, 3H, ArCH₃), 2.23 (s, 3H, ArCH₃), 3.01 (s, 6H,N(CH₃)₂) 119 2.1 (s, 3H, ArCH₃), 2.2 (s, 3H, ArCH₃), 2.6 (s, 3H, SCH₃),3.0 (s, 6H, N(CH₃)₂ 121 2.15 (s, 3H, ArCH₃), 2.39 (s, 3H, ArCH₃), 2.99(s, 6H, N(CH₃)₂), 3.42 (s, 3H, NCH₃) 123 1.4 (s, 9H, C(CH₃)3) 2.2 (s,3H, ArCH₃), 2.25 (s, 3H, ArCH₃), 3.0 (s, 6H, N(CH₃)₂) 124 0.88 (t, 3H,CH₂CH₃), 1.27 (d, 3H, CHCH₃), 1.66 (m, 2H, CHCH ₂CH₃, 2,14 (s, 3H,ArCH₃), 2.20 (s, 3H, ArCH₃), 3.01 (s, 6H, N(CH₃)₂), 3.19 (m, 1H, CHCH₃)125 2.10 (s, 3H, ArCH₃), 2.18 (s, 3H, ArCH₃), 3.00 (s, 6H, N(CH₃)₂) 1262.20-2.22 (m, 9H, ArCH₃, CH═CCH₃), 3.04 (S, 6H, N(CH₃)₂) 128 2.26 (s,3H, ArCH₃), 2.30 (s, 3H, ArCH₃), 3.00 (s, 6H, N(CH₃)₂), 4.07 (s, 2H,NCH₂) 129 1.10 (t, 6H, NCH₂CH₃)₂), 2.12 (s, 3H, ArCH₃), 2.20 (s, 3H,ArCH₃), 3.00 (s, 6H, N(CH₃)₂), 3.22 (q, 4H, N(CH ₂CH₃)₂) 130 0.82 (t,3H, CHCH₃), 1.21 (d, 3H, CHCH₃), 1.57 (q, 2H, CH ₂CH₃), 2.10 (s, 3H,ArCH₃), 2.19 (s, 3H, ArCH₃), 2.54 (q, 1H, CHCH₃), 3.01 (s, 6H, N(CH₃)₂)134 2.20 (s, 3H, ArCH₃), 2.23 (s, 3H, ArCH₃), 3.02 (s, 6H, N(CH₃)₂), 1352.08 (s, 3H, ArCH₃), 2.22 (s, 3H. ArCH₃), 3.04 (s, 6H, N(CH₃)₂) 136 2.10(s, 3H, ArCH₃), 2.20 (s, 3H, ArCH₃), 2.90-3.00 (m, 12H, 2xN(CH₃)₂) 1372.1 (s, 3H, ArCH₃), 2.2 (s, 3H, ArCH₃), 3.0 (s, 6H, N(CH₃)₂) 138 2.2 (s,3H, ArCH₃), 2.3 (s, 3H, ArCH₃), 3.1 (s, 6H, N(CH₃)₂) 139 2.10 (s, 3H,ArCH₃), 2.20 (s, 3H, ArCH₃), 3.01 (s, 6H, N(CH₃)₂) 140 1.35 (t, 3H,OCH₂CH₃), 2.05 (s, 3H, ArCH₃), 2.20 (s, 3H, ArCH₃) 2.28 (s, 3H, SCH₃),3.00 (s, 6H, N(CH₃)₂), 4.35 (q, 2H, OCH ₂CH₃) 141 2.20 (s, 3H, ArCH₃),2.25 (s, 3H, ArCH₃), 3.05 (s, 6H, NCH₃) 142 2.10 (s, 3H, ArCH₃), 2.20(s, 3H, ArCH₃), 2.95 (s, 6H, N(CH₃)₂) 143 1.85 (s, 3H, N═CCH₃), 2.05 (s,3H, ArCH₃), 2.10 (s, 3H, ArCH₃), 3.05 (s, 6H, NCH₃) 148 2.09 (s, 3H,ArCH₃), 2.26 (s, 3H, ArCH₃), 3.01 (s, 6H, N(CH₃)₂), 149 1.20 (d, 6H,CH(CH₃)₂), 2.12 (s, 3H, ArCH₃), 2.20 (s, 3H, ArCH₃), 2.85 (m, 1H,CH(CH₃)₂), 3.00 (s, 6H, N(CH₃)₂) 150 2.09 (s, 3H, ArCH₃), 2.20 (s, 3H,ArCH₃), 2.57 (s, 3H, COCH₃), 3.03 (s, 6H, N(CH₃)₂) 151 0.75 (s, 9H,C(CH₃)₃), 1.35 (s, 6H, C(CH₃)₂), 1.70 (s, 2H, CCH₂C), 2.10 (s, 3H,ArCH₃), 2.20 (s, 3H, ArCH₃), 3.00 (s, 6H, N(CH₃)₂) 152 1.21 (d, 6H,CH(CH₃)₂), 2.10 (s, 3H, ArCH₃), 2.20 (s, 3H, ArCH₃), 2.83 (m, 1H,CH(CH₃)₂), 3.00 (s, 6H, N(CH₃)₂) 153 2.15 (s, 3H, ArCH₃), 2.3 (s, 3H,3.0, ArCH₃), 3.00 (s, 6H, N(CH₃)₂) 154 0.9 (m, 9H, CH₃(CH₂)3), 1.6 (m,2H, CH₂), 2.05 (s, 3H, ArCH₃) 2.15 (s 3H, ArCH₃) 2.74 (m, 2H, ArCH₂) 3.0(s, 6H, N(CH₃)₂) 155 2.25 (s, 6H, ArCH₃), 2.55 (s, 6H, ArCH₃) 3.05 (s,6H, N(CH₃)₂) 156 2.0 (s, 3H, ArCH₃), 2.2 (s, 3H, ArCH₃), 3.0 (s, 6H,N(CH₃)₂) 3.8 (s, 2H, CH₂) 157 1.95 (s, 3H, ArCH₃), 2.2 (s, 3H, ArCH₃),3.0 (s, 6H, N(CH₃)₂) 3.85 (s, 2H, CH₂) 158 1.95 (s, 3H, ArCH₃), 2.2 (s,3H, ArCH₃), 3.0 (s, 6H, N(CH₃)₂), 3.85 (m, 5H, OCH₃, CH₂) 159 2.3 (s,6H, ArCH₃), 3.0 (s, 6H, N(CH₃)₂) 160 2.2 (s, 6H, ArCH₃), 3.0 (s, 6H,N(CH₃)₂) 161 1.2-1.9 (m, 10H, cyCH₂) 2.1 (s, 3H, ArCH₃), 2.2 (s, 3H,ArCH₃) 2.6 (m, 1H, CH) 3.0 (s, 6H, N(CH₃)₂) 162 2.2 (s, 3H, ArCH₃), 2.3(s, 3H, ArCH₃) 3.05 (s, 6H, N(CH₃)₂) 163 2.2 (s, 3H, ArCH₃) 2.3 (s, 3H,ArCH₃), 3.05 (s, 6H, N(CH₃)₂) 164 2.2 (s, 3H, ArCH₃), 2.3 (s, 3H,ArCH₃), 3.05 (s, 6H, N(CH₃)₂) 165 2.15 (s, 3H, ArCH₃), 2.25 (s, 3H,ArCH₃), 2.5 (s, 3H, CH₃) 2.75 (s, 3H, CH₃) 3.0 (s, 6H, N(CH₃)₂) 166 2.1(s, 3H, ArCH₃), 2.25 (s, 3H, ArCH₃), 3.0 (s, 6H, N(CH₃)₂), 3.7 (s, 3H,CH₃) 167 2.2 (s, 3H, ArCH₃), 2.25 (s, 3H, ArCH₃), 3.05 (s, 6H, N(CH₃)₂)168 2.15 (s, 3H, ArCH₃). 2.25 (s, 3H, ArCH₃) 3.0 (s, 6H, N(CH₃)₂, 4.15(s, 3H, OCH₃) 169 2.2 (s, 3H, ArCH₃) 2.25 (s, 3H, ArCH₃) 3.0 (s, 6H,N(CH₃)₂) 170 0.70 (t, 3H, CH₂CH₃), 1.25 (s, 6H, C(CH₃)₂), 1.60 (q, 2H,CH ₂CH₃), 2.10 (s, 3H, ArCH₃), 2.20 (s, 3H, ArCH₃), 3.00 (s, 6H, NCH₃)171 1.20 (t, 3H, CH₂CH₃), 2.15 (s, 3H, ArCH₃), 2.20 (s, 3H, ArCH₃), 2.60(q, 2H, CH ₂CH₃), 3.00 (s, 6H, N(CH₃)₂) 172 0.70 (t, 3H, CH₂CH₃), 1.25(s, 6H, CH₃), 1.60 (q, 2H, CH ₂CH₃), 1.80 (s, 3H, N═CCH₃), 2.00 (s, 3H,ArCH₃), 2.10 (s, 3H, ArCH₃), 3.00 (s, 6H, N(CH₃)₂) 173 2.09 (s, 3H,ArCH₃), 2.20 (s, 3H, ArCH₃), 2.30 (s, 3H, ArCH₃), 3.01 (s, 6H, N(CH₃)₂)174 2.10 (s, 3H, ArCH₃), 2.19 (s, 9H, ArCH₃), 3.01 (s, 6H, N(CH₃)₂) 1762.23 (s, 3H, ArCH₃), 2.35 (s, 3H, ArCH₃), 3.02 (s, 6H, N(CH₃)₂) 177 2.22(s, 3H, ArCH₃), 2.34 (s, 3H, ArCH₃), 3.01 (s, 6H, N(CH₃)₂), 6.74 (d, 1H,thiophH), 6.84 (d, 1H, thiophH) 180 0.45-1.75 (m, 19H, C₉H₁₉), 2.10 (s,3H, ArCH₃), 2.18 (s, 3H, ArCH₃), 3.00 (s, 6H, N(CH₃)₂) 181 1.21 (t, 3H,CH₂CH₃), 2.10 (s, 3H, ArCH₃), 2.20 (s, 3H, ArCH₃), 2.60 (q, 2H, CH₂CH₃), 3.01 (s, 6H, N(CH₃)₂) 182 2.15 (s, 3H, ArCH₃), 2.22 (s, 3H,ArCH₃), 3.04 (s, 6H, N(CH₃)₂) 183 2.10 (s, 3H, ArCH₃), 2.20 (s, 3H,ArCH₃), 3.02 (s, 6H, N(CH₃)₂) 184 2.10 (s, 3H, ArCH₃), 2.20 (s, 3H,ArCH₃), 3.01 (s, 6H, N(CH₃)₂), 2.40 (s, 3H, SCH₃) 185 2.10 (s, 3H,ArCH₃), 2.20 (s, 3H, ArCH₃), 3.02 (s, 6H, N(CH₃)₂) 186 1.60 (s, 6H,C(CH₃)₂), 2.00 (s, 3H, ArCH₃), 2.10 (s, 3H, ArCH₃), 2.95 (s, 6H,N(CH₃)₂) 190 2.10 (s, 3H, ArCH₃), 2.20 (s, 3H, ArCH₃), 3.00 (s, 6H,N(CH₃)₂) 191 1.00 (t, 6H, N(CH₂CH₃)₂), 1.76 (s, 3H, N═CCH₃), 1.97 (s,3H, ArCH₃), 2.18 (s, 3H, ArCH₃), 3.00 (s, 6H, N(CH₃)₂), 3.35 (m, 4H,N(CH₂)₂) 196 2.16 (s, 3H, ArCH₃), 2.19 (s, 3H, ArCH₃), 2.96 (s, 6H,N(CH₃)₂) 197 2.20 (s, 3H, ArCH₃), 2.23 (s, 3H, ArCH₃), 3.02 (s, 6H,N(CH₃)₂) 198 1.20 (d, 6H, CHCH₃)₂), 2.00 (s, 3H, ArCH₃), 2.05 (s, 3H,ArCH₃), 2.10 (s, 3H, ArCH₃), 2.95 (s, 6H, N(CH₃)₂), 3.30 (q, 1H,CH(CH₃)₂) 199 1.25 (d, 3H, CHCH₃), 1.85 (s, 3H, ═CCH₃), 2.00 (s, 3H,ArCH₃), 2.15 (s, 3H, ArCH₃), 2.20 (s, 3H, ArCH₃), 3.05 (s, 6H, N(CH₃)₂),3.40 (q, 1H, CHCH₃) 200 1.10 (t, 3H, CH₂CH₃), 2.05 (s, 3H, ArCH₃), 2.15(s, 3H, ArCH₃), 2.60 (s, q, 2H, CH ₂CH₃), 2.95 (s, 6H, N(CH₃)₂) 201 1.15(t, 3H, CH₂CH₃), 1.80 (s, 3H, ═CCH₃), 1.95 (s, 3H, ArCH₃), 2.05 (s, 3H,ArCH₃), 2.65 (q, 2H, CH ₂CH₃), 3.00 (s, 6H, N(CH₃)₂) 202 2.10 (s, 3H,ArCH₃), 2.20 (s, 3H, ArCH₃), 2.233 (s, 3H, ArCH₃), 2.40 (s, 3H, SCH₃),3.01 (s, 6H, N(CH₃)₂) 203 2.10 (s, 3H, ArCH₃), 2.22 (s, 3H, ArCH₃), 3.02(s, 6H, N(CH₃)₂) 204 1.20 (t, 3H, CH₂CH₃), 2.08 (s, ArCH₃), 2.20 (s,ArCH₃), 2.92 (q, CH ₂CH₃), 3.02 (s, 6H, N(CH₃)₂) 207 2.30 (s, 3H, ArCH₃)3.05 (s, 6H, N(CH₃)₂) 208 1.20 (s, 6H, CH(CH₃)₂) 2.20 (s, 3H, ArCH₃)3.05 (s, 6H, N(CH₃)₂), 3.30 (q, 1H, CH(CH₃)₂) 209 1.85 (s, 3H, NCCH₃)2.10 (s, 3H, ArCH₃) 3.10 (s, 6H, N(CH₃)₂) 210 1.47 (s, 9H, C(CH₃)₃),2.32 (s, 3H, ArCH₃), 3.04 (s, 6H, N(CH₃)₂) 213 2.13 (s, 3H, ArCH₃), 2.20(s, 3H, ArCH₃), 3.00 (s, 6H, N(CH₃)₂) 214 2.2 (s, 3H, ArCH₃), 2.3 (s,3H, ArCH₃), 3.0 (s, 6H, N(CH₃)₂), 5.2 (s, 1H, CHCN) 215 2.16 (s, 3H,ArCH₃), 2.18 (s, 3H, ArCH₃), 2.97 (s, 6H, N(CH₃)₂) 216 2.10-2.25 (m, 9H,ArCH₃), 3.00 (s, 6H, N(CH₃)₂) 217 2.17 (s, 3H, ArCH₃), 2.18 (s, 3H,ArCH₃), 2.99 (s, 6H, N(CH₃)₂), 3.78 (s, 3H, OCH₃) 219 2.10 (s, 3H,ArCH₃), 2.22 (s, 3H, ArCH₃), 3.02 (s, 6H, N(CH₃)₂) 220 2.20 (s, 6H,ArCH₃), 3.01 (s, 6H, N(CH₃)₂), 5.18 (s, 2H, ArCH₂O) 221 2.10 (s, 3H,ArCH₃), 2.19 (s, ArCH₃), 3.00 (s, 6H, N(CH₃)₂), 5.92 (s, 2H, OCH₂O) 2222.10 (s, 3H, ArCH₃), 2.20 (s, 3H, ArCH₃), 2.27 (s, 6H, ArCH₃), 3.01 (s,6H, N(CH₃)₂) 223 2.10 (s, 3H, ArCH₃), 2.20 (s, 3H, ArCH₃), 3.01 (s, 6H,N(CH₃)₂), 3.73 (s, 6H, OCH₃) 224 2.10 (s, 3H, ArCH₃), 2.25 (s, 3H,ArCH₃), 3.00 (s, 6H, N(CH₃)₂) 225 1.25 (m, 3H, NCH₂CH₃), 2.20 (s, 3H,ArCH₃), 2.25 (s, 3H, ArCH₃), 2.35 (m, 2H, NCH ₂CH₃), 3.00 (s, 3H, NCH₃)227 2.35 (m, 6H, Ar(CH₃)₂) 230 1.22 (d, 6H, CH(CH₃)₂), 1.82 (s, 3H,N═CCH₃), 2.00 (s, 3H, ArCH₃), 2.10 (s, 3H, ArCH₃), 3.03 (s, 6H,N(CH₃)₂), 3.30 (q, 1H, CH(CH₃)₂) 231 2.1 (s, 3H, ArCH₃), 2.15 (s, 3H,ArCH₃), 2.9 (s, 6H, N(CH₃)₂) 3.7 (s, 3H, OCH₃), 5.1 (s, 1H, CHCO₂CH₃)232 1.30 (t, 3H, NCH₂CH₃), 2.30 (m, 8H, Ar(CH₃)₂) + NCH ₂CH₃), 3.45(br,1H, NH) 233 1.47 (s, 9H, C(CH₃)₃), 1.79 (s, 3H, N═CCH₃), 2.15 (s, 3H,ArH), 3.06 (s, 6H, N(CH₃)₂) 235 2.12 (s, 3H, ArCH₃), 2.20 (s, 3H,ArCH₃), 2.50 (m, 1H, CH₂CCH), 3.00 (s, 6H, N(CH₃)₂), 4.60 (d, 2H, CH₂CCH) 236 2.10 (s, 3H, ArCH₃) 2.20 (s, 3H, ArCH₃) 3.00 (s, 6H, N(CH₃)₂)237 1.90 (s, 3H, NCCH₃), 2.30 (s, 3H, ArCH₃), 3.10 (s, 6H, N(CH₃)₂) 2381.75 (s, 3H, N═CCH₃), 1.95 (s, 3H, ArCH₃), 2.02 (s, ArCH₃), 3.00 (s, 6H,N(CH₃)₂) 239 1.15 (t, 3H, CH₂CH₃), 1.75 (s, 3H, N═CCH₃), 1.95 (s, 3H,ArCH₃), 2.05 (s, ArCH₃), 2.54 (q, 2H, CH ₂CH₃), 3.00 (s, 6H, N(CH₃)₂)240 1.75 (s, 3H, N═CCH₃), 1.95 (s, 3H, ArCH₃), 2.05 (s, ArCH₃), 3.00 (s,6H, N(CH₃)₂) 241 1.75 (s, 3H, N═CCH₃), 1.95 (s, 3H, ArCH₃), 2.02 (s,ArCH₃), 3.00 (s, 6H, N(CH₃)₂) 242 1.80 (s, 3H, N═CCH₃), 1.95 (s,3HArCH₃), 2.02 (s, 3H, ArCH₃), 2.40 (s, 3H, SCH₃), 3.00 (s, 6H, N(CH₃)₂)243 1.75 (s, 3H, N═CCH₃), 1.95 (s, 3H, ArCH₃), 2.00 (s, ArCH₃), 3.00 (s,6H, N(CH₃)₂) 244 1.75 (s, 3H, N═CCH₃), 1.95 (s, 3H, ArCH₃), 2.00 (s,ArCH₃), 3.00 (s, 6H, N(CH₃)₂) 245 1.15 (t, 3H, CH₂CH₃), 1.78 (s, 3H,N═CCH₃), 1.93 (s, 3H, ArCH₃), 1.99 (s, ArCH₃), 2.88 (s, 2H, CH ₂CH₃),3.00 (s, 6H, N(CH₃)₂) 246 1.70 (m, 6H, CH₂CH₂CH₂), 2.20 (s, 3H, ArCH₃),2.25 (s, 3H, ArCH₃), 3.50 (m, 4H, CH₂NCH₂) 247 2.3 (s, 3H, ArCH₃), 3.04(s, 6H, N(CH₃)₂) 248 0.20 (s, 9H, Si(CH₃)₃), 2.05 (s, 3H, ArCH₃), 2.15(s, 3H, ArCH₃), 2.95 (s, 6H, N(CH₃)₂) 249 2.10 (s, 3H, ArCH₃), 2.20 (s,3H, ArCH₃), 3.00 (s, 6H, N(CH₃)₂) 3.1 (s, 1H, CCH) 251 1.15 (d, 6H,CH(CH₃)₂), 2.15 (s, 3H, ArCH₃), 2.20 (s, 3H, ArCH₃), 2.30 (s, 3H,ArCH₃), 3.00 (s, 6H, N(CH₃)₂) 3.30 (q, 1H, CH(CH₃)₂) 254 1.00 (t, 3H,CH₂CH₃), 2.10 (s, 3H, ArCH₃), 2.20, (s, 3H, ArCH₃), 2.25 (q, 2H, CH₂CH₃), 3.05 (s, 6H, N(CH₃)₂) 255 1.05 (t, 3H, CH₂CH₃), 2.20 (s, 3H,ArCH₃), 2.30 (m, 2H, CH ₂CH₃), 3.00 (s, 6H, N(CH₃)₂) 256 1.10 (d, 6H,CH(CH₃)₂), 2.05 (s, 3H, ArCH₃), 2.10 (s, 3H, ArCH₃), 2.20 (s, 3H,ArCH₃), 2.95 (s, 6H, NCH₃) 3.30 (q, 1H, CH(CH₃)₂) 257 0.85 (s, 9H,C(CH₃)₃), 3.00 (s, 6H, N(CH₃)₃) 268 2.10 (s, 3H, ArCH₃), 2.21 (s, 3H,ArCH₃), 3.01 (s, 6H, N(CH₃)₂) 260 1.00 (s, 9H, C(CH₃)₃), 3.05 (S. 6H,N(CH₃)₂) 261 2.15 (s, 3H, ArCH₃), 2.20 (s, 3H, ArCH₃), 3.00 (s, 6H,N(CH₃)₂), 5.00 (s, 2H, (OCH₂Ph) 262 2.15 (s, 3H, ArCH₃), 2.25 (s, 3H,ArCH₃), 3.00 (s, 6H, N(CH₃)₂) 263 2.10 (s, 3H, ArCH₃), 2.18 (s, 3H,ArCH₃), 3.03(s, 6H, 2N(CH₃)₂ 265 2.15 (s, 3H, ArCH₃), 2.10 (s, 3H,ArCH₃), 3.00 (s, 6H, N(CH₃)₂) 266 2.15 (s, 3H, ArCH₃), 2.10 (s, 3H.ArCH₃), 3.00 (s, 6H, N(CH₃)₂), 5.00 (s, 2H, CH₂) 267 0.9-1.3 (m, 5H),1.6-1.8 (m ,6H), 2.1 (s 3H), 2.15 (s, 3H), 3.6 (d, 2H), 2.95 (d, 6H) 2682.1 (s, 3H, ArCH₃), 2.2 (s, 3H, ArCH₃), 2.9 (s, 6H, N(CH₃)₂), 4.2 (m,4H, O(CH₂)₂O) 269 1.2 (s, 9H, C(CH₃)₃), 2.1 (s, 3H, ArCH₃) 2.15 (s, 3H,ArCH₃), 2.9 (s, 6H, N(CH₃)₂) 4.1-4.25 (br, 4H, O(CH₂)₂O) 270 1.85-2.0(m, 4H, CH₂CH₂) 2.1 (s, 3H, ArCH₃), 2.15 (s, 3H, ArCH₃), 2.9 (s, 6H,N(CH₃)₂), 3.8-4.0 (m, 4H, OCH₂, OCH₂) 271 1.65-1.9 (m, 4H, (CH₂)₂, 2.1(s, 3H, ArCH₃), 2.2 (s, 3H, ArCH₃), 2.9 (s, 6H, N(CH₃)₂), 3.65-3.9 (m,4H, OCH₂, NCH₂) 272 1.4-1.8 (m, 6H, (CH₂)₃), 2.1 (s, 3H, ArCH₃), 2.2 (s,3H, ArCH₃), 2.9 (s, 6H, N(CH₃)₂), 3.8 (m, 4H, OCH₂, ArCH₂) 273 1.2 (s,9H, C(CH₃)₃), 1.90 (m, 2H, CH₂), 2.1 (s, 3H, ArCH₃), 2.2 (s, 3H, ArCH₃),2.9 (s, 6H, N(CH₃)₂), 3.95-4.1 (m, 4H, (CH₂)₃) 274 1.1-1.2 (m, 2H, CH₂),1.3 (s, 9H, C(CH₃)₃), 1.9-2.0 (m, 2H, CH₂), 2.1 (s, 3H, ArCH₃), 2.2 (s,3H, ArCH₃), 2.9 (s, 6H, N(CH₃)₂), 3.9-4.0 (m, 4H, OCH₂, OCH₂) 275 1.25(s, 9H, C(CH₃)₃), 1.9 (brs, 4H, (CH₂)₂), 2.1 (s, 3H, ArCH₃), 2.2 (s, 3H,ArCH₃), 2.9 (s, 6H, N(CH₃)₂), 3.8-4.0 (br.d, 4H, O(CH₂), OCH₂) 2761.35-1.8 (m, 6H, (CH₂)₃), 2.1 (d, 6H, Ar(CH₃)₂), 2.9 (s, 6H, N(CH₃)₂),3.45 (m, 1H, CH), 3.6-4.0 (m, 4H, OCH₂, OCH₂) 277 2.1 (s, 3H, ArCH₃),2.2 (s, 3H, ArCH₃), 2.2 (s, 2H, CH₂), 2.9 (s, 6H, N(CH₃)₂), 4.05 (m, 2H,CH₂), 4.1 (m, 2H, CH₂) 278 1.2-1.8 (m, 20H, (CH₂)₁₀), 2.05 (s, 3H,ArCH₃), 2.2 (s, 3H, ArCH₃), 2.9 (s, 6H, N(CH₃)₂), 3.3 (m, 1H, CH), 3.45(m, 1H, CH), 3.7 (m, 1H, CH), 3.8-3.9 (m, 3H, CH + CH₂), 4.5 (m, 1H, CH)279 2.15 (d, 6H, (ArCH₃)₂), 2.9 (s, 6H, N(CH₃)₂), 3.6 (s, 3H, OCH₃),3.75 (s, 3H, COOCH₃), 4.8 (s, 2H, CH₂) 280 2.05 (s, 3H, ArCH₃), 2.15 (s,3H, ArCH₃), 2.9 (s, 6H, N(CH₃)₂), 3.0 (m, 2H, CH₂), 4.05 (m, 2H, CH₂)281 0.95 (t, 3H, CH₂CH₃), 1.30 (s, 9H, CCH₃), 1.65 (q, 2H, CH ₂CH₃),2.20 (s, 3H, ArCH₃), 2.25 (s, 3H, ArCH₃), 3.05 (s, 3H, NCH₃), 3.30 (m,2H, NCH₂) 282 0.90 (t, 3H, CH₂CH₃), 1.20 (s, 9H, CCH₃), 1.30 (m,2HCH₂CH₂), 1.50 (m, 2H, CH₂CH₂), 2.05 (s, 3H, ArCH₃), 2.10 (s, 3H,ArCH₃), 2.90 (s, 3H, NCH₃), 3.20 (m, 2H, NCH₂) 283 1.25 (d, 6H,CH(CH₃)₂), 1.30 (s, 9H, C(CH₃)₃), 2.15 (s, 3H, ArCH₃), 2.20 (s, 3H,ArCH₃), 2.90 (s, 3H, N(CH₃)₂), 3.70 (m, 1H, CH(CH₃)₂) 284 1.30 (s, 9H,C(CH₃)₃), 2.20 (s, 3H, ArCH₃), 2.25 (s, 3H, ArCH₃), 3.00 (s, 3H, NCH₃),3.95 (m, 2H, NCH₂), 5.25 (d, 2H, CH═CH ₂), 5.90 (m, 1H, CH═CH₂) 285 1.00(t, 3H, CH₂CH₃), 1.25 (t, 3H, CH₂CH₃), 1.30 (s, 9H, C(CH₃)₃), 1.40 (q,2H, CH ₂CH₃), 1.65 (m, 2H, CH₂CH₂), 2.20 (s, 3H, ArCH₃), 2.25 (s, 3H,ArCH₃), 3.40 (m, 4H, NCH₂, NCH₂) 286 1.15 (t, 6H, (CH₂CH₃)₂), 1.20 (s,9H, C(CH₃)₃), 2.05 (s, 3H, ArCH₃), 2.15 (s, 3H, ArCH₃), 3.35 (m, 4H,N(CH ₂CH₃)₂) 287 1.50 (s, 9H, C(CH₃)₃), 2.00 (s, 3H, ArCH₃) 2.20 (s, 3H,ArCH₃), 2.95 (s, 6H, N(CH₃)₂) 288 1.21 (m, 9H, CH ₂CH₃, C(CH₃)₃), 2.15(d, 6H, ArCH₃), 3.00 (s, 6H, N(CH₃)₃), 3.61 (m, 1H, CH ₂CH₃), 3.05 (s,6H, N(CH₃)₂), 3.92 (m, 1H, CH ₂CH₃) 289 1.20-1.80 (m, 10H, C₅H₁₀), 2.05(s, 3H, ArCH₃), 2.20 (s, 3H, ArCH₃), 3.00 (s, 6H, N(CH₃)₂), 3.90 (m, 1H,SCH) 290 0.80-2.00 (m, 11H, C₆H₁₁), 2.15 (s, 3H, ArCH₃), 2.18 (s, 3H,ArCH₃), 3.00 (s, 6H, N(CH₃)₂), 3.70 (d, 2H, OCH₂C₆H₁₁) 291 1.30 (d, 6H,CH(CH₃)₂), 2.10 (s, 3H, ArCH₃), 2.20 (s, 3H, ArCH₃), 3.00 (s, 6H,N(CH₃)₂), 4.45 (m, 1H, CH(CH₃)₂), 292 2.22 (s, 3H, ArCH₃), 3.00 (s, 6H,N(CH₃)₂), 4.20 (t, 2H, OCH₂CH₂O), 4.35 (t, 2H, OCH₂CH₂O) 294 3.00 (s,6H, N(CH₃)₂) 295 2.00 (m, 6H, (ArCH₃)₂), 2.95 (m, 6H, N(CH₃)₂), 3.30 (m,2H, ArCH₂CH₂), 4.05 (m, 2H, ArCH₂CH₂) 296 2.10 (s, 3H, ArCH₃), 2.20 (s,3H, ArCH₃), 3.00 (s, 6H, N(CH₃)₂), 5.05 (s, 2H, ArCH₂O) 297 1.25 (s, 9H,C(CH₃)₃), 3.00 (s, 6H, N(CH₃)₂) 298 2.10 (s, 3H, ArCH₃), 2.15 (s, 3H,ArCH₃), 3.05 (s, 6H, N(CH₃)₂) 301 2.10 (s, 3H, ArCH₃), 2.20 (s, 3H,ArCH₃), 3.00 (s, 6H, N(CH₃)₂), 5.05 (s, 2H, ArCH₂O) 302 0.90 (d, 6H,CH(CH₃)₂), 1.70 (m, 2H, CH ₂CH(CH₃)₂), 1.78 (m, 1H, CH(CH₃)₂), 2.15 (s,6H, Ar(CH₃)₂), 3.00 (s, 6H, N(CH₃)₂), 4.03 (t, 2H, OCH ₂CH₂) 303 1.33(d, 6H, CH(CH₃)₂), 2.15 (s, 3H, ArCH₃), 2.20 (s, 3H, ArCH₃), 3.00 (s,6H, N(CH₃)₂), 4.42 (m, 1H, CH(CH₃)₂) 304 1.00 (s, 9H, C(CH₃)₃), 2.10 (s,3H, ArCH₃), 2.15 (s, 3H, ArCH₃) 3.15 (s, 6H, N(CH₃)₂) 305 2.20 (s, 6H,Ar(CH₃)₂), 3.00 (s, 6H, N(CH₃)₂), 5.20 (s, 2H, ArCH₂O) 306 2.22 (s, 3H,ArCH₃), 3.00 (s, 6H, N(CH₃)₂), 5.15 (s, 2H, ArCH₂O) 310 1.20 (t, 3H,CH₂CH₃), 2.10 (s, 3H, ArCH₃), 2.25 (s, 3H, ArCH₃), 3.00 (s, 3H, NCH₃),3.40 (m, 2H, CH ₂CH₃) 311 1.25 (m, 9H, CH₂CH₃ + CH(CH₃)₂), 2.15 (s, 3H,ArCH₃), 2.25 (s, 3H, ArCH₃), 2.90 (q, 1H, CH(CH₃)₂), 3.05 (s, 3H, NCH₃),3.40 (m, 2H, CH ₂CH₃) 312 1.25 (t, 3H, CH₂CH₃), 2.10 (s, 3H, ArCH₃),2.20 (s, 3H, ArCH₃), 3.00 (s, 3H, NCH₃), 3.40 (m, 2H, CH ₂CH₃), 3.75 (s,3H, OCH₃) 313 0.70 (t, 3H, CH₂CH₃), 1.25 (t, 3H, CH ₂CH₃), 1.30 (s, 6H,C(CH₃)₂), 1.65 (q, 2H, CH ₂CH₃), 2.15 (s, 3H, ArCH₃), 2.20 (s, 3H,ArCH₃), 3.00 (s, 3H, NCH₃), 3.40 (b, 2H, NCH₂) 314 0.70-1.70 (m, 24H,C₁₀H₂₁ + CHCH₃), 2.02 (s, 3H, ArCH₃), 2.10 (s, 3H, ArCH₃), 2.95 (s, 6H,N(CH₃)₂), 4.20 (m, 1H, OCH(CH₃)C) 315 1.30 (d, 6H, CH(CH₃)₂), 2.18 (s,6H, Ar(CH₃)₂), 3.00 (s, 6H, N(CH₃)₂), 4.55 (m, 1H, CH(CH₃)₂) 316 1.10(d, 12H, CH(CH₃)₂), 2.00 (s, 3H, ArCH₃), 2.10 (s, 3H, ArCH₃), 3.00 (s,6H, N(CH₃)₂) 317 2.10 (s, 3H, ArCH₃), 2.19 (s, 3H, ArCH₃), 2.26 (s, 3H,ArCH₃), 3.01 (s, 6H, N(CH₃)₂), 3.47 (s, 3H, OCH₃) 318 2.10 (s, 3H,ArCH₃) 2.19 (s, 3H, ArCH₃), 3.00 (s, 6H, N(CH₃)₂) 319 0.75-1.85 (m, 24H,C₁₀H₂₁ + CHCH₃), 2.18 (s, 6H, Ar(CH₃)₂), 3.00 (s, 6H, N(CH₃)₂), 4.38 (m,1H, C₁₀H₂₁CHCH₃) 320 0.90 (d, 6H, CH(CH₃)₂), 1.60 (t, 2H, OCH₂ CH ₂CH),1.70 (m 1HCH(CH₃)₂), 2.20 (s, 3H, ArCH₃), 3.00 (s, 6H, N(CH₃)₂), 4.00(t, 2H, OCH ₂CH₂) 321 1.30 (d, 6H, CH(CH₃)₂), 2.25 (s, 3H, ArCH₃), 3.00(s, 6H, N(CH₃)₂), 4.50 (m, 1H, CH(CH₃)₂) 323 2.20 (m, 6H, ArCH₃),8.60-8.35 (m, 1H, NH) 324 1.30 (s, 9H, C(CH₃)₃), 2.25 (m, 6H, ArCH₃),8.30-8.60 (m, 1H, NH) 325 1.25 (t, 3H, CH₂CH₃), 2.15 (s, 3H, ArCH₃),2.25 (s, 3H, ArCH₃), 3.00 (s, 3H, NCH₃), 3.40 (m, 2H, CH ₂CH₃) 326 1.30(s, 9H, C(CH₃)₃)), 1.25 (t, 3H, CH₂CH₃), 2.15 (s, 3H, ArCH₃), 2.25 (s,3H, ArCH₃), 3.00 (s, 3H, NCH₃), 3.40 (m, 2H, NCH ₂CH₃) 328 2.20 (s, 3H,ArCH₃), 2.24 (s, 3H, ArCH₃), 3.02 (s, 6H, N(CH₃)₂) 329 2.00 (s, 3H,ArCH₃), 2.15 (s, 3H, ArCH₃), 2.95 (s, 3H, NCH₃), 3.85 (m, 2H, NCH₂),5.15 (d, 2H, CHCH ₂), 5.80 (m, 1H, CHCH₂) 330 1.20 (d, 3H, CH(CH₃)₂),2.00 (s, 3H, ArCH₃), 2.15 (s, 3H, ArCH₃), 2.85 (s, 3H, NCH₃), 3.60 (m,1H, CHCH₃) 331 0.90 (t, 3H, CH₂CH₃), 1.30 (m, 2H, CH₂CH₂), 1.55 (m, 2H,CH₂CH₂), 2.00 (s, 3H, ArCH₃), 2.15 (s, 3H, ArCH₃), 2.95 (s, 3H, NCH₃),3.20 (m, 2H, NCH₂) 334 2.10 (s, 3H, ArCH₃), 2.20 (s, 3H, ArCH₃), 3.00(s, 6H, N(CH₃)₂) 335 1.25 (t, 3H, CH₂CH₃), 2.10 (s, 3H, ArCH₃), 2.25 (s,3H, ArCH₃), 3.00 (s, 3H, NCH₃), 3.40 (m, 2H, CH ₂CH₃) 336 2.10 (s, 3H,ArCH₃), 2.20 (s, 3H, ArCH₃),3.00 (s, 6H, N(CH₃)₂) 340 0.93 (d, 6H,CH(CH₃)₂), 1.60 (t, 2H, OCH₂ CH ₂CH), 1.80 (m, 1H, CH(CH₃)₂), 2.10 (s,3H, ArCH₃), 2.20 (s, 3H, ArCH₃), 3.00 (s, 6H, N(CH₃)₂), 3.90 (t, 2H, OCH₂CH₂) 341 0.70-1.85 (m, 11H, C₆H₁₁), 2.05 (s, 3H, ArCH₃), 2.13 (s, 3H,ArCH₃), 2.92 (s, 6H, N(CH₃)₂, 3.60 (d, 2H, OCH₂Ar) 342 2.15 (s, 3H,ArCH₃), 2.23 (s, 3H, ArCH₃), 3.00 (s, 6H, N(CH₃)₂), 5.00 (s, 2H, OCH₂Ar)343 2.10 (s, 3H, ArCH₃), 2.20 (s, 3H, ArCH₃), 2.50 (d, 1H, CH₂CCH), 3.00(s, 6H, N(CH₃)₂), 4.60 (d, 2H, OCH ₂CCH) 344 2.12 (s, 3H, ArCH₃), 2.22(s, 3H, ArCH₃), 3.00 (s, 6H, N(CH₃)₂), 4.45 (d, 2H, OCH₂CHCH ₂),5.22-5.42 (m, 2H, OCH ₂CHCH₂), 6.00 (m, 1H, OCH₂ CHCH₂) 345 2.15 (s, 3H,ArCH₃), 2.20 (s, 3H, ArCH₃), 3.00 (s, 6H, N(CH₃)₂), 4.25 (brs, 4H,ArOCH₂CH₂O) 346 2.15 (s, 3H, ArCH₃), 2.20 (s, 3H, ArCH₃), 3.30 (s, 6H,N(CH₃)₂) 347 1.25 (s, 9H, C(CH₃)₃), 2.10 (s, 3H, ArCH₃), 2.30 (s, 3H,ArCH₃), 3.05 (b, 6H, N(CH₃)₂) 348 0.30 (m, 2H, cyCH₂), 0.60 (m, 2H,cyCH₂), 1.20 (m, 1H, cyCH), 2.10 (s, 3H, ArCH₃), 2.20 (s, 3H, ArCH₃),3.00 (s, 6H, N(CH₃)₂), 3.72 (d, 2H, OCH₂C₃H₅) 349 2.10 (s, 3H, ArCH₃),2.20 (s, 3H, ArCH₃), 3.00 (s, 6H, N(CH₃)₂), 5.20 (s, 2H, COCH₂O) 3502.07 (s, 3H, ArCH₃), 2.20 (s, 3H, ArCH₃), 3.75 (s, 3H, OCH₃), 4.52 (s,2H, COCH₂O) 352 2.10 (s, 3H, ArCH₃), 2.20 (s, 3H, ArCH₃), 3.00 (s, 6H,N(CH₃)₂), 4.60 (s, 2H, COCH₂O), 5.20 (s, 2H, PhCH₂O) 353 2.15 (s, 3H,ArCH₃), 2.20 (s, 3H, ArCH₃), 3.30 (s, 6H, N(CH₃)₂) 354 1.60-2.30 (m, 4H,THF), 2.10 (s, 3H, ArCH₃), 2.20 (s, 3H, ArCH₃), 3.00 (s, 6H, N(CH₃)₂),3.70-4.00 (m, 4H, THF + OCH₂) 4.20 (m, 1H, THF) 355 1.20-1.95 (m, 6H,THP), 2.10 (s, 3H, ArCH₃), 2.20 (s, 3H, ArCH₃), 3.00 (s, 6H, N(CH₃)₂),3.40-4.10 (m, 5H, THP + OCH₂) 357 2.10 (s, 3H, ArCH₃), 2.20 (s, 3H,ArCH₃), 3.00 (s, 6H, N(CH₃)₂) 358 1.10 (t, 3H, OCH₂CH₃), 1.60 (d, 3H,CHCH₃), 2.10 (s, 3H, ArCH₃), 2.20 (s, 3H, ArCH₃), 3.00 (s, 6H, N(CH₃)₂),4.20 (q, 2H, OCH ₂CH₃), 4.60 (q, 1H, CHCH₃) 359 2.10 (s, 3H, ArCH₃),2.20 (s, 3H, ArCH₃), 3.00 (s, 6H, N(CH₃)₂), 4.25 (q, 2H, OCH₂CF₃) 3602.10 (s, 3H, ArCH₃), 2.20 (s, 3H, ArCH₃), 2.40 (m, 4H, OCH₂ CH ₂ CH ₂),3.00 (s, 6H, N(CH₃)₂), 3.40 (t, 2H, CH₂ CH ₂CN) 3.90 (t, 2H, OCH₂(CH₂)₃) 361 2.05 (s, 3H, ArCH₃), 2.20 (s, 3H, ArCH₃), 3.00 (s, 6H,N(CH₃)₂) 362 1.00 (s, 9H, C(CH₃)₃), 2.00 (s, 6H, ArCH₃), 3.00 (s, 6H,N(CH₃)₂) 363 2.20 (s, 3H, ArCH₃), 3.00 (s, 6H, N(CH₃)₂) 364 1.2 (t, 3H,NCH₂CH₃) 2.05 (s, 3H, ArCH₃), 2.2 (s, 3H, ArCH₃), 3 (s, 3H, NCH₃), 3.35(br, 2H, NCH ₂CH₃) 365 2.1 (s, ArCH₃), 2.2 (s, 3H, ArCH₃), 3.0 (s, 6H,N(CH₃)₂) 366 2.1 (s, 3H, ArCH₃), 2.2 (s, 3H, ArCH₃), 3.0 (s, 6H,N(CH₃)₂) 367 2.00 (s, 3H, CH₃CO), 2.10 (s, 3H, ArCH₃), 2.20 (s, 3H,ArCH₃), 2.98 (s, 6H, N(CH₃)₂) 368 2.00 (s, 6H, ArCH₃), 3.00 (s, 6H,N(CH₃)₂) 369 2.10 (s, 3H, ArCH₃), 2.20 (s, 3H, ArCH₃), 2.40 (s, 6H,Het(CH₃)₂), 3.00 (s, 6H, N(CH₃)₂) 370 0.90 (d, 6H, CH₂CH(CH₃)₂), 1.80(m, 1H, CH₂ CH(CH₃)₂), 2.10 (s, 3H, ArCH₃), 2.20 (s, 3H, ArCH₃), 2.40(d, 2H, CH ₂CH(CH₃)₂), 3.00 (s, 6H, N(CH₃)₂) 371 1.60 (s, 6H, C(CH₃)₂),1.95 (s, 3H, ArCH₃), 2.10 (s, 3H, ArCH₃), 2.95 (s, 6H, N(CH₃)₂) 372 1.05(t, 6H, CH(CH₃)_(2), 1.25 (t, 3H, OCH) ₂CH₃), 2.10 (s, 3H, ArCH₃), 2.20(s, 3H, ArCH₃), 2.23 (m, 1H, CH(CH₃)₂), 3.00 (s, 6H, N(CH₃)₂) , 4.20 (q,2H, OCH ₂CH₃) 373 2.1 (s, 3H, ArCH₃) , 2.2 (s, 3H, ArCH₃), 3.35 (s, 3H,NCH₃) 374 1.45 (t, 3H, NCH₂CH₃), 2.15 (s, 3H, ArCH₃), 2.2 (s, 3H,ArCH₃), 3.8 (q, 2H, NCH ₂CH₃) 375 2.15 (s, ArCH₃), 2.25 (s, ArCH₃), 2.6(s, 3H, NC(O)CH₃) 376 1.45 (d, 3H, CHCH₃), 2.10 (s, 3H, ArCH₃), 2.20 (s,3H, ArCH₃), 2.22 (s, 3H, COCH₃), 3.00 (s, 6H, N(CH₃)₂), 4.55 (q, 1H,OCHCH₃) 377 0.93 (m, 6H, (CHCH₂CH₃)₂), 1.60 (m, 4H, (CHCH ₂CH₃)₂), 2.10(s, 3H, ArCH₃), 2.20 (s, 3H, ArCH₃), 3.00 (s, 6H, N(CH₃)₂), 4.00 (m, 1H,OCH) 378 1.5-2.9 (m, 9H, cyp), 2.10 (s, 3H. ArCH₃), 2.20 (s, 3H, ArCH₃),3.30 (s, 6H, N(CH₃)₂) 379 2.10 (s, 3H, ArCH₃), 2.20 (s, 3H, ArCH₃), 3.00(s, 6H. N(CH₃)₂) 380 1.22 (t, 3H, OCH₂CH₃), 2.10 (s, 3H, ArCH₃), 2.20(s, 3H, ArCH₃), 3.00 (s, 6H, N(CH₃)₂), 4.00 (s, 3H, OCH₃), 4.25 (q, 2H,OCH ₂CH₃) 381 2.05 (s, 3H, ArCH₃), 2.20 (s, 3H, ArCH₃), 3.00 (s, 6H,N(CH₃)₂) 382 0.85 (t, 3H, CH₂CH₃), 1.25 (m, 6H, CH₂CH₂), 1.55 (m, 2H,ArCH ₂CH₂), 2.05 (s, 3H, ArCH₃), 2.20 (s, 3H, ArCH₃), 2.50 (t, 2H, CH₂CH₃), 3.00 (s, 6H, NCH₃) 383 2.00 (s, 6H, ArCH₃), 3.00 (s, 6H, N(CH₃)₂)384 2.10 (s, 3H, ArCH₃), 2.20 (s, 3H, ArCH₃), 3.00 (s, 6H, N(CH₃)₂),3.45 (s, 6H, (OCH₃)₂), 3.93 (d, 2H, OCH₂), 4.68 (t, 1H, (CH₃O)₂ CHCH₂)385 1.23 (t, 6H, (CH₃CH₂O)₂), 2.10 (s, 3H, ArCH₃), 2.20 (s, 3H, ArCH₃),3.00 (s, 6H, N(CH₃)₂), 3.55-3.80 (m, 4H, (CH₃ CH ₂O)₂), 3.95 (d, 2H,OCH₂), 4.78 (t, 1H, (CH₃CH₂O)₂ CH) 386 1.32 (s, 9H, C(CH₃)₃), 2.13 (s,3H, ArCH₃), 2.20 (s, 3H, ArCH₃), 3.00 (s, 6H, N(CH₃)₂), 4.30 (m, 4H,OCH₂CH₂O) 388 2.10 (s, 3H, ArCH₃), 2.20 (s, 3H, ArCH₃), 3.00 (s, 6H,N(CH₃)₂) 390 1.30 (s, 6H, PhC(CH₃)₂) 2.05 (s, 3H, ArCH₃), 2.20 (s, 3H,ArCH₃), 2.80 (s, 2H, PhCCH₂), 3.05 (s, 6H, N(CH₃)₂) 391 1.55 (s, 6H,C(CH₃)₂), 2.10 (s, 3H, ArCH₃), 2.20 (s, 3H, ArCH₃), 3.05 (s, 6H,N(CH₃)₂) 392 1.50 (s, 6H, C(CH₃)₂), 2.10 (s, 3H, ArCH₃), 2.20 (s, 3H,ArCH₃), 3.00 (s, 6H, N(CH₃)₂), 3.05 (s, 3H, OCH₃) 393 1.25 (t, 3H,CH₂CH₃), 2.10 (s, 3H, ArCH₃), 2.25 (s, 3H, ArCH₃), 3.00(s, 3H, NCH₃)3.40 (b, 2H, CH₂CH₃) 394 2.00 (s, 3H, ArCH₃,) 2,10 (s, 3H, ArCH₃), 2.20(s, 3H, ArCH₃), 3.00 (s, 6H, N(CH₃)₂) 395 1.20 (t, 3H, CH₂CH₃), 2.10 (s,3H, ArCH₃), 2.20 (s, 3H, ArCH₃), 2.40 (s, 3H, ArCH₃), 3.00 (s, 3H,N(CH₃), 3.40 (br, 2H, NCH₂) 396 1.30 (s, 9H, C(CH₃)₃), 1.90 (m, 4H,CH₂CH₂), 2.15 (s, 3H, ArCH₃), 2.25 (s, 3H, ArCH₃), 3.5 (m, 4H, CH₂NCH₂)397 2.10 (s, 3H, ArCH₃), 2.20 (s, 3H, ArCH₃) 3.00 (s, 6H, N(CH₃)₂)

The following compounds of formula Ib (see Table 3), i.e. compounds ofgeneral formula I where R¹ is hydrogen, R³ is methyl, R⁴ is methyl, R⁵is methyl substituted at the 5-position of the phenyl ring, —A—R⁶ ispara to the amidine moiety and is 3-Bu^(t)-phenoxy, may be prepared bymethods analogous to those of Examples 1 to 17 Where the moiety depictedon the right side of linkage A is attached to R⁶.

TABLE 3 Cmp R² m.p./° C. 501 1-Me-piperidin-4-yl oil 5022-dimethylaminoethyl oil 503 ethoxycarbonylmethyl oil 504 propargyl oil505 2,2-dimethoxyethyl oil 506 2-hydroxyethyl oil 507 cyclopropyl oil508 cyclohexyl oil

Those compounds in Table 3 which do not have discrete melting pointshave the characteristic ¹H N.M.R shown in Table 4 below.

TABLE 4 Cmp Data 501 1.25 (s, 9H, C(CH₃)₃), 1.70-2.05 (m, 8H, cyCH₂),2.10 (s, 3H, ArCH₃), 2.15 (s, 3H, ArCH₃), 2.30 (s, 3H, NCH₃), 2.90 (s,3H, NCH₃) 502 1.20 (s, 9H, C(CH₃)₃), 2.10 (s, 3H, ArCH₃), 2.20 (s, 3H,ArCH₃), 2.25 (s, 6H, CH₂N(CH₃)₂), 2.45 (m, 2H, NCH₂), 3.00 (s, 3H,NCH₃), 3.40 (m, 2H, NCH₂) 503 1.00 (t, 3H, CH₂CH₃), 1.30 (s, 9H,C(CH₃)₃), 2.15 (s, 3H, ArCH₃), 2.20 (s, 3H, ArCH₃) 3.10 (s, 3H, NCH₃),4.15 (s, 2H, NCH₂), 4.25 (q, 2H, CH ₂CH₃) 504 1.30 (s, 9H, C(CH₃)₃),2.15 (s, 3H, ArCH₃), 2.20 (s, 2H, ArCH₃), 2.30 (s, 1H, CHC), 3.10 (s,3H, NCH₃), 4.20 (s, 2H, NCH₂) 505 1.30 (s, 9H, C(CH₃)₃), 2.20 (s, 3H,ArCH₃), 2.25 (s, 3H, ArCH₃), 3.15 (s, 3H, NCH₃), 3.50 (s, 6H, OCH₃),3.60 9(m, 2H, NCH₂), 4.60 (m, 1H, CH) 506 1.20 (s, 9H, C(CH₃)₃), 2.10(s, 3H, ArCH₃), 2.20 (s, 3H, ArCH₃), 3.05 (s, 3H, NCH₃), 3.55 (s, 2H,OCH₂), 3.80 (s, 2H, NCH₂), 5.95 (m, 1H, OH) 507 1.30 (s, 9H, C(CH₃)₃),0.60 (s, 2H, cyCH₂), 0.70 (s, 2H, cyCH₂), 2.10 (s, 3H, ArCH₃), 2.20 (s,3H, ArCH₃) 508 0.85-1.90 (m, 10H, cyCH₂), 1.30 (s, 9H, C(CH₃)₃), 2.15(s, 3H, CH₃), 2.20 (s, 3H, ArCH₃), 3.00 (s, 3H, NCH₃)

EXAMPLE 18 N,N-Dimethyl-N′-[4-(3-trifluoromethyl %henoxy)-2,5-xylyl]formamidine sulfate salt

(Compound 602)

To a solution of the compound 1 (see Table 1) (0.3 g) in ethanol (0.3ml) was added dropwise concentrated sulfuric acid (0.098 g). The mixturewas filtered and the resulting solid was washed with diethyl ether togive the title compound as a solid, m.p. 178-80° C.

The following compounds of formula X (see Table 4), i.e. salts ofgeneral formula I where —A—R⁶ is para to the amidine moiety, R¹ ishydrogen, R⁴ is methyl, An is an anion and u is 1 or 2 depending on thevalency of the anion, may be prepared by methods analogous to Example18.

TABLE 4 Cmp R² R³ (R⁵)_(m) A R⁶ An⁻ m.p./° C. 600 Me Me 5-Me —OCH₂—3-CF₃-phenyl sulfate 215-7 601 Me Me 5-Me, O 3-CF₃-phenyl sulfate 114-86-Br 602 Me Me 5-Me O 3-CF₃-phenyl sulfate 178-80 603 Me Me 5-Me O3-CF₃-phenyl chloride 152-4 604 Me Me 5-Me O 3-CF₃-phenylp-toluenesulfonate 133-5 605 Me Me 5-Me O 3-CF₃-phenyl saccharinate oil606 Me Me 5-Me O 3-CF₃-phenyl trifluoroacetate 141-3 607 Me Me 5-Me O3-CF₃-phenyl methanesulfonate 151-3 608 Me Me 5-Me O 3-CF₃-phenyloxalate 184-6 609 Me Me 5-Me O 3-CF₃-phenyl camphorsulfonate oil 610—(CH₂)₄— 5-Me O 3-CF₃-phenyl chloride 159-63 611 Me Me 5-Me O3-Ph-1,2,4- chloride 80 thiadiazol-5-yl

Those compounds in Table 4 which do not have discrete melting pointshave the following characteristic ¹H N.M.R. data in CDCl₃.

Compound 605

¹H N.M.R. δ(ppm) 2.15 (s, 3H, ArCH₃), 2.25 (s, 3H, ArCH₃), 3.20 (s, 3H,N(CH₃)), 3.25 (s, 3H, N(CH₃)), 10.20-10.80 (br, 1H, NH)

Compound 609

¹H N.M.R. δ(ppm) 0.75 (s, 3H, CCH₃), 1.05 (s, 3H, CCH₃), 1.25 (d, 2H,CH₂), 1.75-1.95 (m, 3H), 2.15 (s, 3H, ArCH₃), 2.20 (m, 1H, CH), 2.25 (s,3H, ArCH₃), 2.35 (d, 1H, CH), 2.60 (t, 1H, CH), 2.85 (d, 1H, CH), 3.20(s, 3H, N(CH₃), 3.30 (s, 3H, N(CH₃).

The following compounds of formula Ic (see Table 5), i.e. compounds ofgeneral formula I where R¹ and R⁵ are hydrogen, R², R³ and R⁴ aremethyl, may be prepared by methods analogous to those of Examples 1 to17. Where the moiety depicted on the right side of linkage A is attachedto R⁶.

TABLE 5 Data (m.p./° C. Cmp Pos^(n) of -A-R⁶ A R6 or 1H N.M.R) 700 5—OCH₂— 3-CF₃-phenyl 2.00 (s, 3H, ArCH₃), 3.00 (s, 6H, N(CH₃)₂), 5.05 (s,2H, ArCH₃) 701 5 —OCH₂— 4-Bu^(t)-phenyl 85-7 ° C. 702 3 —O— 3-CF₃-phenyl2.10 (s, 3H, ArCH₃), 3.00 (s, 6H, N(CH₃)₂)Test Examples

Compounds were assessed for activity against one or more of thefollowing:

-   -   Phytophthora infestans: late tomato blight    -   Plasmopara viticola: vine downy mildew    -   Erysiphe graminis f. sp. tritici: wheat powdery mildew    -   Pyricularia oryzae: rice blast    -   Leptosphaeria nodorum: glume blotch

Aqueous solutions or dispersions of the compounds at the desiredconcentration, including a wetting agent, were-applied by spray or bydrenching the stem base of the test plants, as appropriate. After agiven time, plants or plant parts were inoculated with appropriate testpathogens before or after application of the compounds as appropriate,and kept under controlled environmental conditions suitable formaintaining plant growth and development of the disease. After anappropriate time, the degree of infection of the affected part of theplant was visually estimated. Compounds are assessed on a score of 1 to3 where 1 is little or no control, 2 is moderate control and 3 is goodto total control. At a concentration of 500 ppm (w/v) or less, thefollowing compounds scored 2 or more against the fungi specified.

Phytophthora infestans

7, 8, 28, 30, 36, 46, and 271.

Plasmopara viticola

149, 331, 373 and 364.

Erysiphe graminis f. sp. Tritici

1-5, 7-9, 11-13, 15-24, 26, 2841, 43, 45, 46, 48, 51, 52, 55, 56, 58,59, 61, 62, 65, 68, 76, 84, 86, 90, 100, 101, 104-106, 109, 112, 113,120, 123, 124, 130, 135, 138, 139, 140, 141, 143, 146, 149, 160, 166,171, 173-175, 183, 187-190, 193-196, 200, 203-205, 207-209, 213,215-217, 223, 225, 228, 231, 232, 234, 237, 246, 250, 252, 253, 256,258, 259, 261, 262, 264, 266-272, 277, 279, 281, 282, 284, 286-288, 290,291, 295, 298, 299, 301, 303, 310-312, 318, 325, 326, 330, 331, 335,346, 347, 349, 351, 353, 355-357, 359, 361, 364, 365-368, 370-372, 374,376-379, 392, 396, 398, 502, 504, 600, 601, 610 and 611.

Pyricularia oryzae

7, 17, 20, 21, 23, 26-28, 30, 32, 34, 36, 38, 41, 43, 45, 51, 54, 55,59, 63, 94, 140, 143, 146, 163, 225, 325, 352, 353, 360, 368, 600 and611.

Leptosphaeria nodorum

1, 2, 5, 7, 8, 15, 27, 29, 35, 37, 41, 43, 45, 48, 56, 59, 61, 72, 100,130, 160, 170, 181, 194, 208, 214, 235, 246, 283, 284, 290, 303, 310,311, 312, 325, 326, 351, 364, 369, 378 and 392

1. A compound of formula I and salts thereof

wherein R¹ is hydrogen, optionally substituted alkyl, optionallysubstituted alkenyl, optionally substituted alkynyl, optionallysubstituted carbocyclyl and optionally substituted heterocyclyl; each ofR² and R³, which may be the same or different, is any group defined forR¹, or together with the nitrogen to which they are attached form aring, which may be substituted; R⁴ is selected from the group consistingof alkyl, alkenyl, alkynyl, carbocyclyl and heterocyclyl, each of whichmay be substituted; m is 1; R⁵ is any group defined for R⁴ attached tothe 5-position of the benzene ring M; R⁶ is optionally substitutedcarbo- or heterocyclyl; and A is selected from the group consisting of adirect bond, —O—, —S—, —NR⁹—, —CHR⁷—, and —O—CHR⁷—; where R⁹ is selectedfrom the group consisting of alkyl, alkenyl and alkynyl, each of whichmay be substituted by a member of the group consisting of alkoxy,haloalkoxy, alkylthio, halogen and optionally substituted phenyl; whereR⁷ is selected from the group consisting of alkyl, alkenyl and alkynyl,which may be substituted by a member of the group consisting of alkoxy,haloalkoxy, alkylthio, halogen and phenyl optionally substituted by amember of the group consisting of alkyl, haloalkyl, alkoxy, haloalkoxyand alkylthio; where —A—R⁶ is in the 4-position of the benzene ring Mand the moiety depicted on the right side of linkage A is attached toR⁶, or —A—R⁶ and R⁵ together with benzene ring M form an optionallysubstituted fused ring system.
 2. The compound of claim 1, wherein R¹ isalkyl or hydrogen; each of R² and R³, which may be the same ordifferent, is selected from the group consisting of hydrogen, alkyl,alkenyl and carbocyclyl; R⁴ is alkyl or alkenyl, m is 1; R⁵ is any groupdefined for R⁴ attached to the 5-position of the benzene right M; R⁶ isoptionally substituted carbo- or heterocyclyl; and A is selected fromthe group consisting of a direct bond, —O—, —S—, and NR⁹—, where R⁹ isselected from the group consisting of —CHR⁷—, —O—CHR⁷—, optionallysubstituted alkyl, optionally substituted alkenyl and optionallysubstituted alkynyl, where said substitution group is selected from thegroup consisting of alkoxy, haloalkoxy, alkylthio, halogen andoptionally substituted phenyl; where R⁷ is selected from the groupconsisting of hydroxy, halogen, cyano, acyl, alkoxy, haloalkoxy,alkylthio, optionally substituted alkyl, optionally substituted alkenyl,and optionally substituted alkynyl, where said substitution group isselected from the group consisting of alkoxy, haloalkoxy, alkylthio,halogen and phenyl optionally substituted by a member of the groupselected from alkyl, haloalkyl, alkoxy, haloalkoxy and alkylthio; andwhere —A—R⁶ is in the 4-position of the benzene ring M and the moietydepicted on the right side of linkage A is attached to R⁶; or —A—R⁶ andR⁵ together with benzene ring M form an optionally substituted fusedring system.
 3. The compound of claim 2 wherein R¹ is hydrogen; R² andR³, which may be the same or different, are alkyl or alkenyl; R⁴ isalkyl; m is 1; R⁵ is any group defined for R⁴ attached to the 5-positionof the benzene ring M; R⁶ is optionally substituted carbo- orheterocyclyl; and A is —O—; where —A—R⁶ is in the 4-position of thebenzene ring M and the moiety depicted on the right side of linkage A isattached to R⁶.
 4. The compound of claim 1, which is selected from thegroup consisting of:N′-[4-(3-tert-butylphenoxy)-2,5-dimethylphenyl]-N,N-dimethylimidoformamide,N′-[4-(3-tert-butylphenoxy)-2,5-dimethylphenyl]-N-ethyl-N-methylimidoformamide,N-allyl-N′-[4-(3-tert-butylphenoxy)-2,5-dimethylphenyl]-N-methylimidoformamide,N′-(4-{[4-(2-chlorophenyl)-1,3-thiazol-2-yl]oxy}-2,5-dimethylphenyl)-N,N-dimethylimidoformamide,N′-[2,5-dimethyl-4-(3-phenoxyphenoxy)phenyl]-N-ethyl-N-methylimidoformamide,N′-{4-[4-chloro-3-(trifluoromethyl)phenoxy]-2,5-dimethylphenyl}-N,N-dimethylimidoformamide,N′-{4-[4-chloro-3-(trifluoromethyl)phenoxy]-2,5-dimethylphenyl}—N-ethyl-N-methylimidoformamide,N′-{4-[3-(1-methoxy-1-methylethyl)phenoxy]-2,5-dimethylphenyl}-N,N-dimethylimidoformamide,andN-ethyl-N′-{4-[4-fluoro-3-(trifluoromethyl)phenoxy]-2,5-dimethylphenyl}—N-methylimidoformamide.5. A fungicidal composition comprising at least one compound as claimedin claim 1, in admixture with an agriculturally acceptable diluent orcarrier.
 6. A method of combating fungi at a locus infested or liable tobe infested therewith, which comprises applying to the locus a compoundof formula I or a salt thereof

wherein R¹ is hydrogen, optionally substituted alkyl, optionallysubstituted alkenyl, optionally substituted alkynyl, optionallysubstituted carbocyclyl and optionally substituted heterocyclyl; each ofR² and R³, which may be the same or different, is any group defined forR¹, or together with the nitrogen to which they are attached form aring, which may be substituted; R⁴ is selected from the group consistingof alkyl, alkenyl, alkynyl, carbocyclyl and heterocyclyl, each of whichmay be substituted; m is 1; R⁵ is any group defined for R⁴ attached tothe 5-position of the benzene ring M; R⁶ is optionally substitutedcarbo- or heterocyclyl; and A is selected from the group consisting of adirect bond, —O—, —S—, —NR⁹—, —CHR⁷—, and —O—CHR⁷—; where R⁹ is selectedfrom the group consisting of alkyl, alkenyl and alkynyl, each of whichmay be substituted by a member of the group consisting of alkoxy,haloalkoxy, alkylthio, halogen and optionally substituted phenyl; whereR⁷ is selected from the group consisting of alkyl, alkenyl and alkynyl,which may be substituted by a member of the group consisting of alkoxy,haloalkoxy, alkylthio, halogen and phenyl optionally substituted by amember of the group consisting of alkyl, haloalkyl, alkoxy, haloalkoxyand alkylthio; where —A—R⁶ is in the 4-position of the benzene ring Mand the moiety depicted on the right side of linkage A is attached toR⁶, or —A—R⁶ and R⁵ together with benzene ring M form an optionallysubstituted fused ring system.
 7. The method of claim 6, wherein R¹ isselected from the group consisting of alkyl, alkenyl and alkynyl, eachof which may be substituted by a member of the group consisting ofalkoxy, haloalkoxy, alkylthio, halogen and optionally substitutedphenyl.
 8. The method of claim 6, wherein R¹ is hydrogen.
 9. The methodof claim 6, wherein R¹ is C₁-C₁₀ alkyl.
 10. The method of claim 6,wherein each of R² and R³, which may be the same or different, isselected from the group consisting of alkyl, alkenyl and alkynyl, eachof which may be substituted by a member of the group consisting ofalkoxy, haloalkoxy, alkylthio, halogen, and optionally substitutedphenyl.
 11. The method of claim 6, wherein each of R² and R³, which maybe the same or different, is C₁-C₁₀ alkyl or hydrogen.
 12. The method ofclaim 6, wherein R⁴ is selected from the group consisting of alkyl,alkenyl and alkynyl, each of which may be substituted by a member of thegroup consisting of alkoxy, haloalkoxy, alkylthio, halogen andoptionally substituted phenyl.
 13. The method of claim 6, wherein R⁴ isC₁-C₁₀, alkyl or halogen.
 14. The method of claim 6, wherein R⁵ isselected from the group consisting of alkyl, alkenyl and alkynyl, eachof which may be substituted by a member of the group consisting ofalkoxy, haloalkoxy, alkylthio, halogen and optionally substitutedphenyl.
 15. The method of claim 6, wherein, when present, R⁷ is selectedfrom the group consisting of alkyl, alkenyl, and alkynyl, each of whichmay be substituted by a member of the group consisting of alkoxy,haloalkoxy, alkylthio, halogen, and phenyl optionally substituted by amember selected from the group consisting of alkyl, haloalkyl, alkoxy,haloalkoxy, and alkylthio.
 16. The method of claim 6, wherein, whenpresent, R⁷ is selected from the group consisting of hydroxy, halogen,cyano, acyl, alkoxy, haloalkoxy, alkylthio and hydrogen.
 17. The methodof claim 6, wherein R⁶ is optionally substituted phenyl or optionallysubstituted aromatic heterocyclyl.
 18. The method of claim 6, wherein R⁶is substituted by one or more substituents, which may be the same ordifferent, and selected from the group consisting of alkyl, alkenyl,alkynyl, carbo- and heterocyclyl, each of which may be substituted. 19.The method of claim 6, wherein R⁶ is substituted by one or moresubstituents, which may be the same or different, and selected from thegroup consisting of hydroxy, mercapto, azido, nitro, halogen, cyano,acyl, optionally substituted amino, cyanato, thiocyanato, —SF₅, —OR^(a);—SR^(a) and —Si(R^(a))₃, where R^(a) is selected from the groupconsisting of alkyl, alkenyl, alkynyl, carbocyclyl and heterocyclyl,each of which may be substituted.
 20. The method of claim 6, wherein R⁶is substituted by one or more substituents, which may be the same ordifferent, and selected from the group consisting of hydroxy, halogen,cyano, acyl, amino, alkylamino, dialkylamino, alkyl, haloalkyl,R^(a)O-alkyl, acyloxyalkyl, cyano-oxyalkyl, alkoxy, haloalkoxy,alkylthio, carbocyclyl, and benzyl, where R^(a) is selected from thegroup consisting of alkyl, alkenyl, alkynyl, carbocyclyl andheterocyclyl, each of which may be substituted.
 21. The method of claim20, wherein said R⁶ is substituted by carbocyclyl, which is optionallysubstituted by a member selected from the group consisting of alkyl,haloalkyl, alkoxy, haloalkoxy and alkylthio.
 22. The method of claim 20,wherein said R⁶ is substituted by benzyl, which is optionallysubstituted by a member selected from the group consisting of alkyl,haloalkyl, alkoxy, haloalkoxy and alkylthio.